WO2010022388A2 - Catalysts and methods for polymer synthesis - Google Patents

Catalysts and methods for polymer synthesis Download PDF

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Publication number
WO2010022388A2
WO2010022388A2 PCT/US2009/054773 US2009054773W WO2010022388A2 WO 2010022388 A2 WO2010022388 A2 WO 2010022388A2 US 2009054773 W US2009054773 W US 2009054773W WO 2010022388 A2 WO2010022388 A2 WO 2010022388A2
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WO
WIPO (PCT)
Prior art keywords
group
optionally substituted
membered
nitrogen
sulfur
Prior art date
Application number
PCT/US2009/054773
Other languages
French (fr)
Other versions
WO2010022388A3 (en
Inventor
Scott D. Allen
Anna E. Cherian
Chris A. Simoneau
Jay J. Farmer
Geoffrey W. Coates
Alexei Gridnev
Robert E. Lapointe
Original Assignee
Novomer, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP09791845.2A priority Critical patent/EP2321364B1/en
Priority to BRPI0917785-0A priority patent/BRPI0917785B1/en
Application filed by Novomer, Inc. filed Critical Novomer, Inc.
Priority to PL15180298T priority patent/PL2966108T3/en
Priority to EP15180298.0A priority patent/EP2966108B1/en
Priority to CN200980137885.7A priority patent/CN102164987B/en
Priority to US13/059,967 priority patent/US8633123B2/en
Priority to PL09791845T priority patent/PL2321364T3/en
Priority to KR1020117006527A priority patent/KR101823440B1/en
Priority to KR1020197006248A priority patent/KR102128706B1/en
Priority to ES09791845.2T priority patent/ES2552721T3/en
Priority to KR1020187002261A priority patent/KR101955651B1/en
Priority to JP2011524068A priority patent/JP5832288B2/en
Publication of WO2010022388A2 publication Critical patent/WO2010022388A2/en
Publication of WO2010022388A3 publication Critical patent/WO2010022388A3/en
Priority to US13/755,126 priority patent/US8956989B2/en
Priority to US13/755,112 priority patent/US8951930B2/en
Priority to US13/755,120 priority patent/US8946109B2/en
Priority to US14/615,902 priority patent/US9505878B2/en
Priority to US15/251,668 priority patent/US9951096B2/en
Priority to US15/901,517 priority patent/US10662211B2/en

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    • C—CHEMISTRY; METALLURGY
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
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    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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    • C07C279/12—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/535—Organo-phosphoranes
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0286—Complexes comprising ligands or other components characterized by their function
    • B01J2531/0294—"Non-innocent" or "non-spectator" ligands, i.e. ligands described as, or evidently, taking part in the catalytic reaction beyond merely stabilizing the central metal as spectator or ancilliary ligands, e.g. by electron transfer to or from the central metal or by intra-/intermolecular chemical reactions, e.g. disulfide coupling, H-abstraction
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    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/31—Aluminium
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    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
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    • B01J31/22—Organic complexes
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    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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    • C07C2601/14—The ring being saturated

Definitions

  • Catalysts capable of effecting the copolymerization of epoxides and carbon dioxide to form aliphatic polycarbonates have been known in the art since the 1960s.
  • the early catalysts were based on heterogeneous zinc compounds and suffered from low reactivity, a lack of selectivity for polymer formation vs. cyclic carbonate formation, and a tendency to produce polycarbonates contaminated with ether linkages.
  • the present invention provides, among other things, unimolecular catalyst systems having activity in the copolymerization of carbon dioxide and epoxides and methods of using the same.
  • the present invention provides metal complexes having an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to an active metal center of a metal complex.
  • the present invention provides unimolecular metal complexes and methods for using the same in the copolymerization of carbon dioxide and epoxides.
  • provided metal complexes have the structure:
  • M is a metal atom; comprises a multidentate ligand; (Z) m represents one or more activating moieties attached to the multidentate ligand, where is a linker moiety covalently coupled to the ligand, each Z is an activating functional group; and m is an integer from 1 to 4 representing the number of Z groups present on an individual linker moiety.
  • tethered activating functional groups (Z) are neutral nitrogen-containing moieties.
  • neutral nitrogen-containing moieties are selected from the group consisting of:
  • each occurrence of R 1 , and R 2 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein R 1 and R 2 groups can be taken together with intervening atoms to form one or more optionally substituted
  • each occurrence of R 5 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7- 14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly eye lie saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein an R 5 group can be taken with an R 1 or R 2 group to form one or more optionally substituted rings; and
  • each occurrence of R 7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C 1--20 acyl; C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • tethered activating functional groups (Z) are cationic moieties.
  • cationic moieties are selected from the group consisting of:
  • each occurrence of R 1 , R 2 , and R 3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more R 1 , R 2 , and R 3 groups can be taken together
  • R 4 is hydrogen or -OR 7 ;
  • R 4 is hydrogen, hydroxyl, or optionally substituted C 1--20 aliphatic;
  • each occurrence of R 5 and R 6 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein R 5 and R 6 can be taken together with intervening atoms to form one or more optionally substituted rings optionally
  • each occurrence of R 7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C 1--20 acyl; C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
  • each occurrence of R 8 , R 9 , and R 10 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more R 8 , R 9 and R 10 groups can be taken together with interven
  • each occurance of R 11 is independently selected from the group consisting of: halogen, -NO 2 , -CN, -SR y , -S(O)R y , -S(O) 2 R y , -NR y C(O)R y , -OC(O)R y , -CO 2 R y , -NCO, -N 3 , -OR 7 , -OC(O)N(R y ) 2 , -N(R y ) 2 , -NR y C(O)R y , -NR y C(O)OR y ; or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocycl
  • X- is any anion
  • Ring A is an optionally substituted, 5- to 10-membered heteroaryl group.
  • an activating functional group (Z) is a phosphorous- containing functional group.
  • a phosphorous-containing functional group is chosen from the group consisting of: phosphines (-PR y 2); Phosphine oxides -P(O)R y 2; phosphinites P(OR 7 )R y 2 ; phosphonites P(OR 7 ) 2 R y ; phosphites P(OR 7 ) 3 ; phosphinates OP(OR 7 )R y 2 ; phosphonates; OP(OR 7 ) 2 R y ; phosphates -OP(OR 7 ) 3 ; phosponium salts ([-PR y 3 ] + ) where the phosphorous-containing functional group may be linked to a metal complex through any available position (e.g. direct linkage via the phosphorous atom, or in some cases via an oxygen atom).
  • a phosphorous-containing functional group is chosen from the group consisting of:
  • R 1 and R 2 are as defined above; and each R 7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C 1--20 acyl; C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and where two
  • phosphorous containing functional groups include those disclosed in The Chemistry of Organophosphorus Compounds. Volume 4. Ter- and Quinquevalent Phosphorus Acids and their Derivatives. The Chemistry of Functional Group Series Edited by Frank R. Hartley (Cranfield University, Cranfield, U.K.). Wiley: New York. 1996. ISBN 0-471-95706-2, the entirety of which is hereby incorporated herein by reference.
  • n is an integer between 1 and 4.
  • the present disclosure encompasses methods for the copolymerization of epoxides and carbon dioxide, such methods comprising contacting one or more epoxides with a catalyst described above in the presence of carbon dioxide.
  • the present disclosure encompasses methods for the formation of cyclic carbonates from epoxides and carbon dioxide, such methods comprising contacting one or more epoxides with a catalyst described above in the presence of carbon dioxide.
  • the present disclosure encompasses methods for the formation of poly ethers, such methods comprising contacting one or more epoxides with a catalyst described above.
  • Certain compounds of the present invention can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers.
  • inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers.
  • the compounds of the invention are enantiopure compounds.
  • mixtures of enantiomers or diastereomers are provided.
  • certain compounds, as described herein may have one or more double bonds that can exist as either a Z or E isomer, unless otherwise indicated.
  • the invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic mixtures of enantiomers.
  • this invention also encompasses compositions comprising one or more compounds.
  • isomers includes any and all geometric isomers and stereoisomers.
  • “isomers” include cis- and trans-isomcrs, E- and Z- isomers, R- and ⁇ -enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention.
  • a compound may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as "stereochemically enriched.”
  • a particular enantiomer may, in some embodiments be provided substantially free of the opposite enantiomer, and may also be referred to as "optically enriched.”
  • “Optically enriched,” as used herein, means that the compound is made up of a significantly greater proportion of one enantiomer. In certain embodiments the compound is made up of at least about 90% by weight of an enantiomer. In some embodiments the compound is made up of at least about 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9% by weight of an enantiomer.
  • the enantiomeric excess of provided compounds is at least about 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9%.
  • enantiomers may be isolated from racemic mixtures by any method known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts or prepared by asymmetric syntheses. See, for example, Jacques, et al.,
  • halo and "halogen” as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodo, -I).
  • aliphatic or "aliphatic group”, as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-30 carbon atoms. In certain embodiments, aliphatic groups contain 1-12 carbon atoms. In certain embodiments, aliphatic groups contain 1-8 carbon atoms. In certain embodiments, aliphatic groups contain 1-6 carbon atoms.
  • aliphatic groups contain 1-5 carbon atoms, in some embodiments, aliphatic groups contain 1-4 carbon atoms, in yet other embodiments aliphatic groups contain 1-3 carbon atoms, and in yet other embodiments aliphatic groups contain 1-2 carbon atoms.
  • Suitable aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.
  • the term aliphatic group encompasses aliphatic groups wherein one or more hydrogen atoms are replaced with a halogen atom.
  • the term aliphatic group encompasses chlorinated or fluorinated aliphatic groups including perfluorinated compounds.
  • epoxide refers to a substituted or unsubstituted oxirane.
  • substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes.
  • Such epoxides may be further optionally substituted as defined herein.
  • epoxides comprise a single oxirane moiety.
  • epoxides comprise two or more oxirane moieties.
  • polymer refers to a molecule of high relative molecular mass, the structure of which comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass.
  • a polymer is comprised of only one monomer species (e.g., polyethylene oxide).
  • a polymer of the present invention is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer of one or more epoxides.
  • cycloaliphatic used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cyclic aliphatic monocyclic, bicyclic, or polycyclic ring systems, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined above and described herein.
  • Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, and cyclooctadienyl.
  • the cycloalkyl has 3-6 carbons.
  • cycloaliphatic also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring.
  • a carbocyclic groups is bicyclic.
  • a carbocyclic group is tricyclic.
  • a carbocyclic group is polycyclic.
  • alkyl refers to saturated, straight- or branched-chain hydrocarbon radicals derived by removal of a single hydrogen atom from an aliphatic moiety. Unless otherwise specified, alkyl groups contain 1-12 carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbon atoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5 carbon atoms, in some embodiments, alkyl groups contain 1-4 carbon atoms, in yet other embodiments alkyl groups contain 1-3 carbon atoms, and in yet other embodiments alkyl groups contain 1-2 carbon atoms.
  • alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.
  • alkenyl denotes a monovalent group derived by the removal of a single hydrogen atom from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond. Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. In certain embodiments, alkenyl groups contain 2-8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2-5 carbon atoms, in some embodiments, alkenyl groups contain 2-4 carbon atoms, in yet other embodiments alkenyl groups contain 2-3 carbon atoms, and in yet other embodiments alkenyl groups contain 2 carbon atoms.
  • Alkenyl groups include, for example, ethenyl, propenyl, allyl, 1,3-butadienyl, butenyl, l-methyl-2-buten-1-yl, allyl, 1,3-butadienyl, allenyl, and the like.
  • alkynyl refers to a monovalent group derived by the removal of a single hydrogen atom from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond. Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms.
  • alkynyl groups contain 2-5 carbon atoms, in some embodiments, alkynyl groups contain 2-4 carbon atoms, in yet other embodiments alkynyl groups contain 2-3 carbon atoms, and in yet other embodiments alkynyl groups contain 2 carbon atoms.
  • Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.
  • Carbocycle and "carbocyclic ring” as used herein, refer to monocyclic and polycyclic moieties wherein the rings contain only carbon atoms. Unless otherwise specified, carbocycles may be saturated, partially unsaturated or aromatic, and contain 3 to 20 carbon atoms.
  • Representative carbocyles include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2,l]heptane, norbornene, phenyl, cyclohexene, naphthalene, and spiro[4.5]decane, to name but a few.
  • aryl used alone or as part of a larger moiety as in “aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic and polycyclic ring systems having a total of six to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members.
  • aryl may be used interchangeably with the term “aryl ring”.
  • aryl refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents.
  • aryl is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like.
  • heteroaliphatic refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, phosphorus, or boron. In certain embodiments, one to six carbon atoms are independently replaced by one or more of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated or partially unsaturated groups.
  • heteroaryl and “heteroar-”, used alone or as part of a larger moiety e.g., “heteroaralkyl”, or “heteroaralkoxy” refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 ⁇ electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms.
  • heteroatom refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen.
  • Heteroaryl groups include, without limitation, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl and pteridinyl.
  • heteroaryl and “heteroar-”, as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring.
  • Nonlimiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazin-3(4 ⁇ )-one.
  • heteroaryl group may be mono- or polycyclic.
  • heteroaryl may be used interchangeably with the terms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any of which terms include rings that are optionally substituted.
  • heteroarylkyl refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.
  • heterocycle As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclic radical”, and “heterocyclic ring” are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7-14-membered bicyclic heterocyclic moiety that is saturated, partially unsaturated, or aromatic and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above.
  • nitrogen includes a substituted nitrogen.
  • the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or + NR (as in N-substituted pyrrolidinyl).
  • a heterocyclic ring can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted.
  • saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl.
  • heterocyclic radical are used interchangeably herein, and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, where the radical or point of attachment is on the heterocyclyl ring.
  • a heterocyclyl group may be mono- or bicyclic.
  • heterocyclylalkyl refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions independently are optionally substituted.
  • acyl refers to a group having a formula -C(O)R where R is hydrogen or an optionally substituted aliphatic, aryl, or heterocyclic group.
  • partially unsaturated refers to a ring moiety that includes at least one double or triple bond.
  • partially unsaturated is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as herein defined.
  • protecting group it is meant that a particular functional moiety, e.g., O, S, or N, is masked or blocked, permitting, if desired, a reaction to be carried out selectively at another reactive site in a multifunctional compound.
  • a protecting group reacts selectively in good yield to give a protected substrate that is stable to the projected reactions; the protecting group is preferably selectively removable by readily available, preferably non-toxic reagents that do not attack the other functional groups; the protecting group forms a separable derivative (more preferably without the generation of new stereogenic centers); and the protecting group will preferably have a minimum of additional functionality to avoid further sites of reaction.
  • oxygen, sulfur, nitrogen, and carbon protecting groups may be utilized.
  • hydroxyl protecting groups include methyl, methoxylmethyl (MOM), methylthiomethyl (MTM), t-butylthiomethyl, (phenyldimethylsilyl)methoxymethyl (SMOM), benzyloxymethyl (BOM), p--methoxybenzyloxymethyl (PMBM), (4- methoxyphenoxy)methyl (p-AOM), guaiacolmethyl (GUM), t-butoxymethyl, 4- pentenyloxymethyl (POM), siloxymethyl, 2-methoxyethoxymethyl (MEM), 2,2,2-trichloroethoxymethyl, bis(2-chloroethoxy)methyl, 2-(trimethylsilyl)ethoxymethyl (SEMOR), tetrahydropyranyl (THP), 3-bromotetrahydropyranyl, tetrahydrothiopyranyl, 1-methoxycyclohexyl, 4-methoxytetrahydropyranyl (MTHP
  • the protecting groups include methylene acetal, ethylidene acetal, 1-t-butylethylidene ketal, 1-phenylethylidene ketal, (4-methoxyphenyl)ethylidene acetal,
  • Amino-protecting groups include methyl carbamate, ethyl carbamante, 9-fluorenylmethyl carbamate (Fmoc), 9-(2-sulfo)fluorenylmethyl carbamate, 9-(2,7-dibromo)fluoroenylmethyl carbamate, 2,7-di-t-butyl-[9-( 10,10-dioxo- 10,10,10,10-tetrahydrothioxanthyl)]methyl carbamate (DBD-Tmoc), 4-methoxyphenacyl carbamate (Phenoc), 2,2,2-trichloroethyl carbamate (Troc), 2-trimethylsilylethyl carbamate (Teoc), 2-phenylethyl carbamate (hZ), l-(l-adamantyl)-l-methylethyl carbamate (Adpoc), l,l-dimethyl-2-haloethyl carbamate,
  • N-dithiasuccinimide Dts
  • N-2,3-diphenylmaleimide N-2,5-dimethylpyrrole
  • N-1, 1,4,4- tetramethyldisilylazacyclopentane adduct STABASE
  • 5-substituted 1,3-dimethyl-1,3,5- triazacyclohexan-2-one 5-substituted 1,3-dibenzyl-1,3,5-triazacyclohexan-2-one
  • 1- substituted 3,5-dinitro-4-pyridone N-methylamine, N-allylamine, N-[2-(trimethylsilyl)ethoxy]methylamine (SEM), N-3-acetoxypropylamine,
  • N-cyclohexylideneamine N-(5 ,5 -dimethyl-3 -oxo- 1 -cyclohexenyl)amine, N-borane derivative, N-diphenylborinic acid derivative, N-[phenyl(pentacarbonylchromium- or tungsten)carbonyl]amine, N-copper chelate, N-zinc chelate, N-nitroamine, N-nitrosoamine, amine N-oxide, diphenylphosphinamide (Dpp), dimethylthiophosphinamide (Mpt), diphenylthiophosphinamide (Ppt), dialkyl phosphoramidates, dibenzyl phosphoramidate, diphenyl phosphoramidate, benzenesulfenamide, o-nitrobenzenesulfenamide ( ⁇ ps), 2,4-dinitrobenzenesulfenamide, pentachlorobenzenesulfenamide, 2-nitro-4
  • protecting groups are detailed herein, however, it will be appreciated that the present invention is not intended to be limited to these protecting groups; rather, a variety of additional equivalent protecting groups can be readily identified using the above criteria and utilized in the method of the present invention. Additionally, a variety of protecting groups are described in Protecting Groups in Organic Synthesis, T. W. Greene and P. G. M. Wuts, 3 rd edition, John Wiley & Sons, 1999, the entirety of which is incorporated herein by reference.
  • radical or “optionally substituted radical” is sometimes used.
  • radical means a moiety or functional group having an available position for attachment to the structure on which the substituent is bound. In general the point of attachment would bear a hydrogen atom if the substituent were an independent neutral molecule rather than a substituent.
  • radical or “optionally-substituted radical” in this context are thus interchangeable with “group” or “optionally-substituted group”.
  • compounds of the invention may contain “optionally substituted” moieties.
  • substituted whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent.
  • an "optionally substituted group'Or “optionally substituted radical” may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position.
  • Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds.
  • stable refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.
  • substituents are shown attached to a bond that crosses a bond in a ring of the depicted molecule. This convention indicates that one or more of the substituents may be attached to the ring at any available position (usually in place of a hydrogen atom of the parent structure). In cases where an atom of a ring so substituted has two substitutable positions, two groups may be present on the same ring atom. Unless otherwise indicated, when more than one substituent is present, each is defined independently of the others, and each may have a different structure. In cases where the substituent shown crossing a bond of the ring is -R, this has the same meaning as if the ring were said to be "optionally substituted" as described in the preceding paragraph.
  • Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are independently halogen; -(CH 2 ) 0-4 R°; -(CH 2 V 4 OR o ;
  • -CH CHPh, which may be substituted with R°; -NO 2 ; -CN; -N 3 ; -(CH 2 )o. 4 N(R o ) 2 ;
  • each R o may be substituted as defined below and is independently hydrogen, C 1-4 aliphatic, -CH 2 Ph, -0(CH 2 )o-iPh
  • Suitable monovalent substituents on R o are independently halogen, -(CH 2 ) 0 _ 2 R ⁇ , -(haloR ⁇ ), -(CH 2 ) 0 _ 2 OH, -(CH 2 ) 0 _ 2 OR ⁇ , -(CH 2 ) 0 _ 2 CH(OR ⁇ ) 2 ; -O(haloR'), -CN, -N 3 , -(CH 2 ) 0 . 2 C(O)R ⁇ , -(CH 2 ) 0 .
  • each R ⁇ is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently selected from C 1- 4 aliphatic, -CH 2 Ph, -0(CH 2 )o-iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • Suitable divalent substituents that are bound to vicinal substitutable carbons of an "optionally substituted” group include: -O(CR * 2 ) 2 - 3 O-, wherein each independent occurrence of R is selected from hydrogen, C 1- 6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • Suitable substituents on the aliphatic group of R * include halogen, -R ⁇ , -(haloR ⁇ ), -OH, -OR ⁇ , -O(haloR'), -CN, -C(O)OH, -C(O)OR ⁇ , -NH 2 , -NHR ⁇ , -NR ⁇ 2 , or -NO 2 , wherein each R ⁇ is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently C 1-4 aliphatic, -CH 2 Ph, -0(CH 2 ) 0-1 Ph, or a 5- 6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include -R f , -NR f 2 , -C(O)R f , -C(O)OR f , -C(O)C(O)R f , -C(O)CH 2 C(O)R f , -S(O) 2 R f ; -S(O) 2 NR f 2 , -C(S)NR f 2 , -C(NH)NR f 2 , or -N(R f )S(O) 2 R f ; wherein each R f is independently hydrogen, C 1- 6 aliphatic which may be substituted as defined below, unsubstituted -OPh, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrence
  • Suitable substituents on the aliphatic group of R f are independently halogen, -R ⁇ , -(haloR ⁇ ), -OH, -OR ⁇ , -O(haloR'), -CN, -C(O)OH, -C(O)OR ⁇ , -NH 2 , -NHR ⁇ , -NR ⁇ 2 , or -NO 2 , wherein each R ⁇ is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently C 1-4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0 _iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • the term “catalyst” refers to a substance the presence of which increases the rate and/or extent of a chemical reaction, while not being consumed or undergoing a permanent chemical change itself.
  • the term “multidentate” refers to ligands having multiple sites capable of coordinating to a single metal center.
  • activating moiety refers to a moiety comprising one or more activating functional groups.
  • an activating moiety improves the catalytic activity of a metal complex.
  • such improved catalytic activity is characterized by higher conversion of starting materials compared to a metal complex lacking an activating moiety.
  • such improved catalytic activity is characterized by higher rate of conversion of starting materials compared to a metal complex lacking an activating moiety.
  • such improved catalytic activity is characterized by higher yield of product compared to a metal complex lacking an activating moiety.
  • the present invention provides, among other things, unimolecular metal complexes for the copolymerization of carbon dioxide and epoxides and methods of using the same.
  • provided metal complexes contain a metal- ligand moiety tethered to one or more activating moieties.
  • an activating moiety comprises a linker and one or more activating functional groups.
  • provided metal complexes act as polymerization catalysts.
  • at least one activating functional group present on the tethered moiety can act as a polymerization co-catalyst and thereby increase the rate of the copolymerization.
  • provided metal complexes include a metal atom coordinated to a multidentate ligand and at least one activating moiety tethered to the multidentate ligand.
  • provided metal complexes have the structure:
  • M is a metal atom
  • (Z) m represents one or more activating moieties attached to the multidentate ligand, where is a linker moiety covalently coupled to the ligand, each Z is an activating functional group; and m is an integer from 1 to 4 representing the number of Z groups present on an individual linker moiety.
  • provided metal complexes include a metal atom coordinated to a multidentate ligand and at least one activating moiety tethered to the multidentate ligand.
  • an activating functional group is selected from the group consisting of neutral nitrogen-containing functional groups, cationic moieties, phosphorous-containing functional groups, and combinations of two or more of these.
  • one or more tethered activating functional groups on provided metal complexes are neutral nitrogen-containing moieties.
  • such moieties include one or more of the structures in Table Z-I : or a combination of two or more of these,
  • each occurrence of R 1 , and R 2 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein two or more R 1 and R 2 groups can be taken together with intervening atoms to form one or more optional
  • each occurrence of R 5 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-
  • each occurrence of R 7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C 1--20 acyl; C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
  • an activating functional group is an N-linked amino
  • R 1 and R 2 are as defined above.
  • R 1 and R 2 are both hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1- 6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted phenyl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro. In some embodiments, R 1 and R 2 are -CF2CF3. In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl.
  • R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y )2-, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • an N-linked amine activating functional group is selected from the group consisting of:
  • one or more activating functional groups is an //-linked
  • R 1 and R 7 are as defined above.
  • R 7 is hydrogen. In some embodiments, R 7 is an optionally substituted radical selected from the group consisting of C 1-12 aliphatic, phenyl, 8- to 10-membered aryl, and 3- to 7-memered heterocyclic. In certain embodiments, R 7 is a C 1-12 aliphatic. In certain embodiments, R 7 is a C 1- 6 aliphatic. In some embodiments, R 7 is an optionally substituted 8- to 10-membered aryl group. In certain embodiments, R 7 is an optionally substituted phenyl. In some embodiments, R 7 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl.
  • R 1 is hydrogen. In some embodiments, R 1 is an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to
  • R 1 is an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • R 1 is an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, R 1 is an optionally substituted C 1--20 aliphatic. In certain embodiments, R 1 is an optionally substituted C 1-12 aliphatic. In some embodiments, R 1 is an optionally substituted C 1- 6 aliphatic. In some embodiments, R 1 is an optionally substituted C 1-12 heteroaliphatic. In some embodiments, R 1 is an optionally substituted 8- to 10-membered aryl. In certain embodiments, R 1 is an optionally substituted phenyl. In some embodiments, R 1 is an optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R 1 is an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 is butyl. In some embodiments, R 1 is isopropyl. In some embodiments, R 1 is phenyl. In some embodiments, R 1 is benzyl.In some embodiments, R 1 is perfluoro. In some embodiments, R 1 is -CF 2 CFs. In certain embodiments, R 1 and R 7 are taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms.
  • one or more N-linked hydroxyl amine activating functional groups are selected from the group consisting of:
  • an activating functional group in a provided metal complex is an amidine.
  • such amidine activating functional groups are an amino acid, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids
  • R 1 , R 2 and R 5 are as defined above.
  • each R 1 and R 2 is hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, each R 1 and R 2 is independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic.
  • each R 1 and R 2 is independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1- 6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro.
  • R 1 and R 2 are -CF 2 CF 3 . In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl. In some embodiments, R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y )2-, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and -CH 2 NR y CH 2 -.
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • R 5 is H. In certain embodiments, R 5 is optionally substituted C 1--20 aliphatic. In some embodiments, R 5 is optionally substituted 6- to 14- membered aryl. In certain embodiments, R 5 is optionally substituted C 1-12 aliphatic. In some embodiments, R 5 is optionally substituted C 1- 6 aliphatic. In certain embodiments, R 5 is optionally substituted phenyl.
  • one or more R 1 or R 2 groups are taken together with R 5 and intervening atoms to form an optionally substituted ring.
  • R 1 and R 5 are taken together to form an optionally substituted 5- or 6-membered ring.
  • R 2 and R 5 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms.
  • R 1 , R 2 and R 5 are taken together to form an optionally substituted fused ring system. In some embodiments such rings formed by combinations of any of R 1 , R 2 and R 5 are partially unsaturated or aromatic.
  • an activating functional group is an //-linked amidine:
  • //-linked amidine groups are selected from the group consisting of:
  • activating functional groups are amidine moieties linked
  • N R 5 N through the imine nitrogen: N R 5 .
  • imine-linked amidine activating functional groups are selected from the group consisting of:
  • activating functional groups are amidine moieties linked
  • carbon-linked amidine activating groups are selected from the group consisting of:
  • one or more activating functional groups is a carbamate.
  • a carbamate is N-linked where R 1 and R 2 are as
  • a carbamate is O-linked: , where R and R 2 are as defined above.
  • R 1 and R 2 are both hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1- 6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro. In some embodiments, R 1 and R 2 are -CF 2 CF 3 . In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl.
  • R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • R 2 is selected from the group consisting of: methyl, t-butyl, t-amyl, benzyl, adamantyl, allyl, 4-methoxycarbonylphenyl, 2-(methylsulfonyl)ethyl, 2-(4-biphenylyl)-prop-2-yl, 2-(trimethylsilyl)ethyl, 2-bromoethyl, and 9-fluorenylmethyl.
  • an activating functional group is a guanidine or bis- guanidine group:
  • each occurrence of R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or
  • R 1 , R 1 , R 2 , R 2 , R 2 - , R 3 , and R 3 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms;
  • each occurrence of R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is hydrogen. In some embodiments, each occurrence of R 1 , R 1 , R 2 , R 2 , R 3 , and R 3 is hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; 3- to 7-membered heterocyclic, phenyl, and 8- to 10- membered aryl.
  • each occurrence of R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is hydrogen or an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • R 2 , R 2 , R 3 , and R 3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic, phenyl, and 8- to 10-membered aryl.
  • each occurrence of R 1 and R 2 is independently an optionally hydrogen or an optionally substituted C 1-8 aliphatic, phenyl, or 8- to 10-membered aryl group.
  • each occurrence of R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is independently hydrogen or an optionally substituted C 1--20 aliphatic.
  • each occurrence of R 1 and R 2 is independently hydrogen an optionally substituted aryl group or an optionally substituted C 1- 8 aliphatic group. In some embodiments, each occurrence of R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is independently hydrogen or an optionally substituted C 1- 6 aliphatic group. In some embodiments, each occurrence of R 1 , R 1 , R 2 , R 2 , R 3 , and R 3 is independently hydrogen or an optionally substituted C 1- 4 aliphatic group.
  • each occurrence of R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 , R 1 , R 2 , R 2 , R 3 , and R 3 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 , R 1' , R 2 , R 2' , R 2 - , R 3 , and R 3' are each independently optionally substituted C 1-6 aliphatic.
  • one or more occurrence of R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, one or more occurrence of R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is independently hydrogen or an optionally substituted phenyl or 8- to 10- membered aryl. In some embodiments, one or more occurrence of R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is independently hydrogen, or an optionally substituted 5- to 10-membered heteroaryl.
  • R 1 is optionally substituted C 1- 6 aliphatic. In certain embodiments, R 1 is optionally substituted C 1-6 aliphatic. In certain embodiments, R 2 is optionally substituted C 1- 6 aliphatic. In certain embodiments, R 2 is optionally substituted C 1- 6 aliphatic. In certain embodiments, R 2 is optionally substituted C 1- 6 aliphatic. In certain embodiments, R is optionally substituted C 1- 6 aliphatic. In certain embodiments, R 3 is optionally substituted C 1- 6 aliphatic.
  • each occurrence of R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl.
  • R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 are each methyl or ethyl.
  • one or more R 1 , R 1 , R 2 , R 2' , R 2- , R 3 , and R 3' is perfluoro.
  • any two or more R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 groups are taken together with intervening atoms to form one or more optionally substituted rings.
  • R 1 and R 2 are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In some embodiments, R 2 and R 2 are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In certain embodiments, R 1 and R 3 are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In some embodiments, [R 2 and R 2 ] and [R 1 and R 3 ] are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms.
  • three or more R 1 , R 1 , R 2 , R 2 , R 2 , R 3 , and R 3 groups are taken together with any intervening atoms to form optionally substituted rings.
  • R 1 and R 2 groups are taken together to form an optionally substituted 5- or 6-membered ring.
  • three or more R 1 and/or R 2 groups are taken together to form an optionally substituted fused ring system.
  • an activating functional group is a guanidine or bis guanidine moiety, it is chosen from the group consisting of:
  • an activating functional group is a urea: where R 1 , and R 2 are as defined above.
  • R 1 and R 2 are each hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1- 6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro.
  • R 1 and R 2 are -CF 2 CF 3 . In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl. In some embodiments, R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y )2-, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and -CH 2 NR y CH 2 -.
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • activating functional groups are oxime or hydrazone
  • R 1 , R 2 , R 5 , and R 7 are as defined above.
  • R 1 and R 2 are both hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, 5- to 14-membered heteroaryl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro. In some embodiments, R 1 and R 2 are -CF2CF3. In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl.
  • R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y )2-, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and -CH 2 NR 7 CH 2 -.
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • R 5 is H. In certain embodiments, R 5 is optionally substituted C 1--20 aliphatic, and in some embodiments R 5 is optionally substituted 6- to 14- membered aryl. In certain embodiments, R 5 is optionally substituted C 1-12 aliphatic and in some embodiments, optionally substituted C 1- 6 aliphatic. In certain embodiments, R 5 is optionally substituted phenyl.
  • one or more R 1 or R 2 groups are taken together with R 5 and intervening atoms to form an optionally substituted ring.
  • R 1 and R 5 are taken together to form an optionally substituted 5- or 6-membered ring.
  • R 2 and R 5 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms.
  • R 1 , R 2 and R 5 are taken together to form an optionally substituted fused ring system. In some embodiments such rings formed by combinations of any of R 1 , R 2 and R 5 are partially unsaturated or aromatic.
  • R 7 is -H. In certain embodiments, R 7 is optionally substituted C 1--20 aliphatic, while in some embodiments R 5 is optionally substituted 6- to 14-membered aryl. In certain embodiments, R 7 is optionally substituted C 1-12 aliphatic or in some embodiments, optionally substituted C 1- 6 aliphatic. In certain embodiments, R 7 is optionally substituted C 1-12 acyl or in some embodiments, optionally substituted C 1- 6 acyl. In certain embodiments, R 7 is optionally substituted phenyl. In some embodiments, R 7 is a hydroxyl protecting group. In some embodiments, R 7 is a silyl protecting group.
  • an activating functional group is an N-oxide derivative:
  • R 1 and R 2 are as defined above. In certain embodiments, R 1 and R 2 are both hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, or 8- to 10- membered aryl and 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1- 6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro. In some embodiments, R 1 and R 2 are -CF 2 CF 3 . In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl.
  • R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y )2-, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and -CH 2 NR y CH 2 -.
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • an JV-oxide activating functional group is selected from the group consisting of:
  • one or more tethered activating functional groups on provided metal complexes are cationic moieties include cationic moieties.
  • such moieties include one or more of the structures in Table Z-2:
  • R 1 , R 2 , and R 3 are as previously defined;
  • R 4 is hydrogen, hydroxyl, optionally substituted C 1--20 aliphatic;
  • each occurrence of R 5 and R 6 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein R 5 and R 6 can be taken together with intervening atoms to form one or more optionally substituted rings optionally
  • each occurrence of R 8 , R 9 , and R 10 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more R 8 , R 9 and R 10 groups can be taken together with intervening
  • X- is any anion
  • Ring A is an optionally substituted, 5- to 10-membered heteroaryl group.
  • a cationic activating functional group is a protonated
  • R 1 and R 2 are both hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, or 8- to 10- membered aryl and 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro. In some embodiments, R 1 and R 2 are -CF2CF3. In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl.
  • R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y )2-, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and -CH 2 NR y CH 2 -.
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • a protonated amine activating functional group is selected from the group consisting of:
  • an activating functional group is a guanidinium
  • each of R 4 , R 5 , R 6 , R 7 , and R 8 is hydrogen.
  • each occurrence of R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen or C 1--20 aliphatic. In some embodiments, each occurrence of R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen or C 1-12 aliphatic. In some embodiments, each occurrence of R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen or C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen or phenyl.
  • each occurrence of R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen or 8- to 10-membered aryl. In some embodiments, each occurrence of R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen or 5- to 10-membered heteroaryl. In some embodiments, each occurrence of R 4 , R 5 , R 6 , R 7 , and R 8 is independently hydrogen or 3- to 7-membered heterocyclic. In some embodiments, one or more of R 4 , R 5 , R 6 , and R 7 is optionally substituted C 1-12 aliphatic.
  • any of (R 4 and R 5 ), (R 5 and R 6 ), (R 6 and R 7 ), (R 7 and R 8 ), and (R 4 and R 7 ) can be taken together with intervening atoms to form one or more optionally substituted rings. In some embodiments, (R 4 and R 5 ) and (R 6 and R 7 ) are taken together to form rings.
  • a guanidinium activating functional group is selected from the group consisting of:
  • an activating functional group is a sulfonium group or an
  • arsonium group , where R 8 , R 9 , and R 10 are as defined above.
  • each occurrence of R 8 , R 9 , and R 10 is independently optionally substituted C 1--20 aliphatic. In some embodiments, each occurrence of R 8 , R 9 , and R 10 is independently hydrogen or optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 9 , R 10 , and R 11 is independently hydrogen or optionally substituted phenyl. In some embodiments, each occurrence of R 9 , R 10 , and R 11 is independently hydrogen or optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 8 , R 9 , and R 10 is independently hydrogen or optionally substituted 5- to 10-membered heteroaryl.
  • each occurrence of R 9 , R 10 , and R 11 is independently hydrogen or optionally substituted 3- to 7-membered heterocyclic.
  • R 8 and R 9 are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 _Ci 4 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted C 6 -CiO aryl, and optionally substituted 5- to 10-membered heteroaryl.
  • R 8 , R 9 and R 10 are each methyl.
  • R 8 , R 9 and R 10 are each phenyl.
  • an arsonium activating functional group is selected from the group consisting of:
  • an activating functional group is an optionally substituted nitrogen-containing heterocycle.
  • the nitrogen-containing heterocycle is an aromatic heterocycle.
  • the optionally substituted nitrogen-containing heterocycle is selected from the group consisting of: pyridine, imidazole, pyrrolidine, pyrazole, quinoline, thiazole, dithiazole, oxazole, triazole, pyrazolem, isoxazole, isothiazole, tetrazole, pyrazine, thiazine, and triazine.
  • a nitrogen-containing heterocycle includes a quaternarized nitrogen atom. In certain embodiments, a nitrogen-containing heterocycle includes an
  • the optionally substituted nitrogen-containing heterocycle is selected from the group consisting of pyridinium, imidazolium, pyrrolidinium, pyrazolium, quinolinium, thiazolium, dithiazolium, oxazolium, triazolium, isoxazolium, isothiazolium, tetrazolium, pyrazinium, thiazinium, and triazinium.
  • a nitrogen-containing heterocycle is linked to a metal complex via a ring nitrogen atom.
  • a ring nitrogen to which the attachment is made is thereby quaternized, and in some embodiments, linkage to a metal complex takes the place of an N-H bond and the nitrogen atom thereby remains neutral.
  • an optionally substituted //-linked nitrogen-containing heterocycle is a pyridinium derivative.
  • optionally substituted N- linked nitrogen-containing heterocycle is an imidazolium derivative.
  • optionally substituted N-linked nitrogen-containing heterocycle is a thiazolium derivative.
  • optionally substituted N-linked nitrogen- containing heterocycle is a pyridinium derivative.
  • an activating functional group is .
  • ring A is an optionally substituted, 5- to 10-membered heteroaryl group.
  • Ring A is an optionally substituted, 6-membered heteroaryl group.
  • Ring A is a ring of a fused heterocycle.
  • Ring A is an optionally substituted pyridyl group.
  • R 12 is hydrogen. In some embodiments, R 12 is an optionally substituted C 1--20 aliphatic group. In some embodiments, R 12 is C 1--20 heteroaliphatic. In some embodiments, R 12 is optionally substituted phenyl, 8- to 10- membered aryl; 5- to 10-membered heteroaryl. In some embodiments, R 12 is 3- to 7- membered heterocyclic. In some embodiments, R 12 is an optionally substituted C 1-12 aliphatic group. In some embodiments, R 12 is neopentyl. In some embodiments, R 12 is oxide or hydroxyl.
  • ring A is other than an imidazole, an oxazole, or a thiazole.
  • a nitrogen-containing heterocycle activating functional group is selected from the group consisting of:
  • an activating functional group is or where R 1 , R 2 and R 5 are as defined above.
  • R 1 and R 2 are each hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1- 6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro. In some embodiments, R 1 and R 2 are -CF2CF3. In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl.
  • R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and -CH 2 NR y CH 2 -.
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • R 5 is H. In certain embodiments, R 5 is optionally substituted C 1--20 aliphatic, and in some embodiments R 5 is optionally substituted 6- to 14- membered aryl. In certain embodiments, R 5 is optionally substituted C 1-12 aliphatic and in some embodiments, optionally substituted C 1- 6 aliphatic. In certain embodiments, R 5 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 5 is perfluoro. In some embodiments, R 5 is-CF 2 CF3.In certain embodiments, R 5 is optionally substituted phenyl.
  • one or more R 1 or R 2 groups are taken together with R 5 and intervening atoms to form an optionally substituted ring.
  • R 1 and R 5 are taken together to form an optionally substituted 5- or 6-membered ring.
  • R 2 and R 5 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms.
  • R 1 , R 2 and R 5 are taken together to form an optionally substituted fused ring system. In some embodiments such rings formed by combinations of any of R 1 , R 2 and R 5 are partially unsaturated or aromatic.
  • an activating functional group is , where R 1 and
  • R 2 are as defined above.
  • R 1 and R 2 are each independently an optionally substituted group selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; phenyl; and 8-10-membered aryl. In some embodiments, R 1 and R 2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R 1 and R 2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-C14 carbocycle, optionally substituted C3-C14 heterocycle, optionally substituted C 6 -CiO aryl, and optionally substituted 5- to 10-membered heteroaryl.
  • R 1 and R 2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R 1 and R 2 is independently perfluoro. In some embodiments, each occurrence of R 1 and R 2 is independently -CF 2 CF 3 .
  • an activating functional group is where R , R , R 3 , and R 5 are as defined above.
  • R 1 , R 2 , and R 3 are each independently an optionally substituted group selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; and 8- 10-membered aryl.
  • R 1 , R 2 , and R 3 are each independently an optionally substituted 4-7-membered heterocyclic.
  • R 1 and R 2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 -Ci 4 carbocycle, optionally substituted C 3 -Ci 4 heterocycle, optionally substituted C 6 -CiO aryl, and optionally substituted 5- to 10-membered heteroaryl.
  • R 1 , R 2 , and R are each independently an optionally substituted C 1-6 aliphatic.
  • R 1 , R 2 , and R 3 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl.
  • R 1 , R 2 , and R 3 are each independently perfluoro.
  • R 1 , R 2 , and R 3 are each independently -CF 2 CF 3 .
  • R 5 is hydrogen. In certain embodiments R 5 is an optionally substituted group selected from the group consisting of C 1- i 2 aliphatic and C 1- i 2 heteroaliphatic. In some embodiments, R 5 is an optionally substituted Cn 2 aliphatic. In some embodiments, R 5 is optionally substituted C 1-6 aliphatic. In some embodiments, an activating functional group is . In certain embodiments, R 1 and R 2 are each independently an optionally substituted group selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; and 8-10- membered aryl. In some embodiments, R 1 and R 2 are each independently an optionally substituted 4-7-membered heterocyclic.
  • R 1 and R 2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 -Ci 4 carbocycle, optionally substituted C 3 -Ci 4 heterocycle, optionally substituted C 6 -CiO aryl, and optionally substituted 5- to 10- membered heteroaryl.
  • R 1 and R 2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl.
  • each occurrence of R 1 and R 2 is independently perfluoro.
  • each occurrence of R 1 and R 2 is independently -CF 2 CF 3 .
  • R 5 and R 6 are each independently an optionally substituted group selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl, and 8-10-membered aryl. In some embodiments, R 5 and R 6 are each independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 5 and R 6 are each independently an optionally substituted C 1--20 heteroaliphatic having. In some embodiments, R 5 and R 6 are each independently an optionally substituted phenyl or 8-10-membered aryl. In some embodiments, R 5 and R 6 are each independently an optionally substituted 5- tolO-membered heteroaryl.
  • R 3 and R 4 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 -Ci 4 carbocycle, optionally substituted C 3 - Ci 4 heterocycle, optionally substituted C 6 -CiO aryl, and optionally substituted 5- to 10- membered heteroaryl.
  • R 5 and R 6 are each independently an optionally substituted C 1-6 aliphatic.
  • each occurrence of R 5 and R 6 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl.
  • each occurrence of R 5 and R 6 is independently perfluoro. In some embodiments, each occurrence of R 5 and R 6 is independently -CF 2 CF 3 . In some embodiments, an activating functional group is where R 1 and R 2 are as defined above.
  • R 1 and R 2 are each hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1- 6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted phenyl or 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro. In some embodiments, R 1 and R 2 are -CF2CF3. In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl.
  • R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y )2-, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and -CH 2 NR y CH 2 -.
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • an activating functional group is I n
  • R 1 , R 2 , and R 3 are each independently an optionally substituted group selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; and 8- 10-membered aryl.
  • R 1 , R 2 , and R 3 are each independently an optionally substituted 4-7-membered heterocyclic.
  • R 1 and R 2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 -C 14 carbocycle, optionally substituted C 3 - C 14 heterocycle, optionally substituted C 6 -CiO aryl, and optionally substituted 5- to 10- membered heteroaryl.
  • R 1 , R 2 , and R 3 are each independently an optionally substituted C 1- 6 aliphatic.
  • R 1 , R 2 , and R 3 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In certain embodiments, R 1 , R 2 , and R 3 are each independently perfluoro. In some embodiments, R 1 , R 2 , and R 3 are each independently - CF 2 CF 3 .
  • an activating functional group is
  • R 1 and R 2 are as defined above.
  • R 1 and R 2 are each hydrogen. In some embodiments, only one of R 1 and R 2 is hydrogen. In certain embodiments, R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic, phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur
  • R 1 and R 2 are each independently an optionally substituted radical selected from the group consisting of C 1-12 aliphatic and C 1-12 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1-12 aliphatic. In some embodiments, R 1 and R 2 are each independently optionally substituted C 1- 6 aliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1--20 heteroaliphatic. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted C 1-12 heteroaliphatic.
  • each occurrence of R 1 and R 2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R 1 and R 2 is independently an optionally substituted 3- to 7-membered heterocyclic.
  • R 1 and R 2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R 1 and R 2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R 1 and R 2 are each butyl. In some embodiments, R 1 and R 2 are each isopropyl. In some embodiments, R 1 and R 2 are perfluoro. In some embodiments, R 1 and R 2 are -CF 2 CF 3 . In some embodiments, R 1 and R 2 are each phenyl. In some embodiments, R 1 and R 2 are each benzyl.
  • R 1 and R 2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 C(R y ) 2 C(R y ) 2 -, -C(R y ) 2 OC(R y ) 2 -, and -C(R y ) 2 NR y C(R y ) 2 -.
  • R 1 and R 2 are taken together to form a ring fragment selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 -, and -CH 2 NR y CH 2 -.
  • R 1 and R 2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms.
  • the resulting nitrogen-containing ring is partially unsaturated.
  • the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
  • an activating functional group is .
  • R 1 and R 2 are each independently an optionally substituted group selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; and 8-10- membered aryl. In some embodiments, R 1 and R 2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R 1 and R 2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-C14 carbocycle, optionally substituted C3-C14 heterocycle, optionally substituted C 6 -CiO aryl, and optionally substituted 5- to 10- membered heteroaryl.
  • R 1 and R 2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R 1 and R 2 is independently perfluoro. In some embodiments, each occurrence of R 1 and R 2 is independently -CF2CF3.
  • an activating functional group is .
  • R 1 , R 2 , and R 3 are each independently an optionally substituted group selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; and 8-
  • R 1 , R 2 , and R 3 are each independently an optionally substituted 4-7-membered heterocyclic.
  • R 1 and R 2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 -C 14 carbocycle, optionally substituted C 3 - C 14 heterocycle, optionally substituted C 6 -CiO aryl, and optionally substituted 5- to 10- membered heteroaryl.
  • R 1 , R 2 , and R 3 are each independently an optionally substituted C 1-6 aliphatic.
  • R 1 , R 2 , and R 3 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In certain embodiments, R 1 , R 2 , and R 3 are each independently perfluoro. In some embodiments, R 1 , R 2 , and R 3 are each independently -
  • an activating functional group is
  • R 1 and R 2 are each independently an optionally substituted group selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; and 8-10-membered aryl. In some embodiments, R 1 and R 2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R 1 and R 2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-C14 carbocycle, optionally substituted C3-C14 heterocycle, optionally substituted C 6 -CiO aryl, and optionally substituted 5- to 10-membered heteroaryl.
  • R 1 and R 2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R 1 and R 2 is independently perfluoro. In some embodiments, each occurrence of R 1 and R 2 is independently -CF 2 CF 3 .
  • X is any anion. In certain embodiments, X is a nucleophile. In some embodiments, X is a nucleophile capable of ring opening an epoxide. In certain embodiments, X is absent. In certain embodiments, X is a nucleophilic ligand.
  • X is -OR X , wherein R x is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.
  • X is -OR X , wherein R x is optionally substituted aryl. In certain embodiments, X is -OR X , wherein R x is optionally substituted phenyl. In certain embodiments, X is -OC 6 H 5 or -OC6H 2 (2,4-NO 2 ).
  • X is halo. In certain embodiments, X is -Br. In certain embodiments, X is -Cl. In certain embodiments, X is -I.
  • X is -O(SO 2 )R X . In certain embodiments X is -OTs. In certain embodiments X is -OSO 2 Me. In certain embodiments X is -OSO 2 CFs. In some embodiments, X is a 2,4-dinitrophenolate anion.
  • activating functional groups Z are phosphorous containing groups.
  • a phosphorous-containing functional group is chosen from the group consisting of: phosphines (-PR y 2); Phosphine oxides -P(O)R y 2; phosphinites P(OR 7 )R y 2; phosphonites P(OR 7 )2R y ; phosphites P(OR 7 )3; phosphinates OP(OR 7 )R y 2 ; phosphonates; OP(OR 7 ) 2 R y ; phosphates -OP(OR 7 ) 3 ; phosponium salts ([-PR y 3] ) where a phosphorous-containing functional group may be linked to a metal complex through any available position (e.g. direct linkage via the phosphorous atom, or in some cases via an oxygen atom).
  • a phosphorous-containing functional group is chosen from the group consisting of:
  • R 1 and R 2 are as defined above;
  • each R 7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C 1--20 acyl; C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and where two R 7 groups can be taken together with intervening atoms
  • phosphorous containing functional groups include those disclosed in The Chemistry of Organophosphorus Compounds. Volume 4. Ter- and Quinquevalent Phosphorus Acids and their Derivatives. The Chemistry of Functional Group Series Edited by Frank R. Hartley (Cranfield University, Cranfield, U.K.). Wiley: New York. 1996. ISBN 0-471-95706-2, the entirety of which is hereby incorporated herein by reference.
  • an activating functional group is a phosphonate group:
  • R 1 , R 2 , and R 7 is as defined above.
  • a phosphonate activating functional group is selected from the group consisting of:
  • an activating functional group is a phosphonic diamide
  • each R 1 and R 2 group in a phosphonic diamide is methyl.
  • an activating functional group is a phosphine group: wherein R 1 , and R 2 are as defined above.
  • a phosphine activating functional group is selected from the group consisting of:
  • each activating moiety (Z) m comprises a linker coupled to at least one activating functional group Z as described above, with m denoting the number of activating functional groups present on a single linker moiety.
  • each activating moiety itself may contain more than one activating functional group Z.
  • each activating moiety contains more than one activating functional groups (i.e. m > 1).
  • each linker moiety contains 1-30 atoms including at least one carbon atom, and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.
  • the linker is an optionally substituted C 2 - 30 aliphatic group wherein one or more methylene units are optionally and independently replaced by
  • R y is independently -H, or an optionally substituted radical selected from the group consisting of C 1-6 aliphatic 3- to 7- membered heterocyclic, phenyl, and 8- to 10- membered aryl.
  • a linker moiety is a C 4 -C 12 aliphatic group substituted with one or more moieties selected from the group consisting of halogen, -NO 2 , -CN, -SR y , -S(O)R y , -S(O) 2 R y , -NR y C(0)R y , -OC(O)R y , -CO 2 R y , -NCO, -N 3 , -OR 7 , -0C(0)N(R y ) 2 , -N(R y ) 2 , -NR y C(0)R y , and -NR y C(0)0R y , where R y is -H, or an optionally substituted radical selected from the group consisting of Ci-6 aliphatic 3- to 7-membered heterocyclic, phenyl, and 8- to 10- membered aryl.
  • a linker moiety is an optionally substituted C 3 _C 3 o aliphatic group. In certain embodiments, a linker is an optionally substituted C 4-24 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 4 - C20 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 4 -C 12 aliphatic group. In certain embodiments, a linker is an optionally substituted C 4 _io aliphatic group. In certain embodiments, a linker is an optionally substituted C 4-8 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 4- C 6 aliphatic group.
  • a linker moiety is an optionally substituted C 6 -C 12 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted Cs aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 7 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 6 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C5 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 4 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C 3 aliphatic group.
  • a aliphatic group in the linker moiety is an optionally substituted straight alkyl chain. In certain embodiments, the aliphatic group is an optionally substituted branched alkyl chain. In some embodiments, a linker moiety is a C 4 to C20 alkyl group having one or more methylene groups replaced by -C(R a R b )- where R a and R b are each, independently C 1 -C 4 alkyl groups. In certain embodiments, a linker moiety consists of an aliphatic group having 4 to 30 carbons including one or more gem-dimethyl substituted carbon atoms.
  • a linker moiety includes one or more optionally substituted cyclic elements selected from the group consisting of saturated or partially unsaturated carbocyclic, aryl, heterocyclic, or heteroaryl.
  • a linker moiety consists of the substituted cyclic element, in some embodiments the cyclic element is part of a linker with one or more non-ring heteroatoms or optionally substituted aliphatic groups comprising other parts of the linker moiety.
  • a linker moiety is of sufficient length to allow one or more activating functional groups to be positioned near a metal atom of a metal complex.
  • structural constraints are built into a linker moiety to control the disposition and orientation of one or more activating functional groups near a metal center of a metal complex.
  • such structural constraints are selected from the group consisting of cyclic moieties, bicyclic moieties, bridged cyclic moieties and tricyclic moieties.
  • such structural constraints are the result of acyclic steric interactions.
  • such structural constraints are selected from the group consisting of cis double bonds, trans double bonds, cis allenes, trans allenes, and triple bonds.
  • such structural constraints are selected from the group consisting of substituted carbons including geminally disubstituted groups such as sprirocyclic rings, gem dimethyl groups, gem diethyl groups and gem diphenyl groups.
  • such structural constraints are selected from the group consisting of heteratom-containing functional groups such as sulfoxides, amides, and oximes.
  • linker moieties are selected from the group consisting of:
  • s is 0. In some embodiments, s is 1. In some embodiments, s is 2. In some embodiments, s is 3. In some embodiments, s is 4. In some embodiments, s is 5. In some embodiments, s is 6.
  • t is 1. In some embodiments, t is 2. In some embodiments, t is 3. In some embodiments, t is 4.
  • the present invention encompasses metal complexes that include a metal atom coordinated to a multidentate ligand and at least one activating moiety tethered to a multidentate ligand.
  • provided metal complexes have the structure:
  • M is a metal atom selected from periodic table groups 3-
  • M is a transition metal selected from periodic table groups 5-12, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 4-11, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 5-10, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 7-9, inclusive. In some embodiments, M is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni. In some embodiments, M is a metal atom selected from the group consisting of: cobalt; chromium; aluminum; titanium; ruthenium, and manganese. In some embodiments, M is cobalt. In some embodiments, M is chromium. In some embodiments, M is aluminum.
  • a metal complex is a zinc, cobalt, chromium, aluminum, titanium, ruthenium, or manganese complex. In certain embodiments, a metal complex is an aluminum complex. In some embodiments, a metal complex is a chromium complex.
  • a metal complex is a zinc complex. In certain some embodiments, a metal complex is a titanium complex. In some embodiments, a metal complex is a ruthenium complex. In certain embodiments, a metal complex is a manganese complex. In certain embodiments, a metal complex is cobalt complex. In certain embodiments where the metal complex is a cobalt complex, the cobalt metal has an oxidation state of 3+ (i.e., Co(III)). In some embodiments, the cobalt metal has an oxidation state of 2+.
  • a metal complex comprises a metal atom coordinated to a single tetradentate ligand and in some embodiments, the metal complex comprises a chelate containing a plurality of individual ligands. In certain embodiments, a metal complex contains two bidentate ligands. In some embodiments, a metal complex contains a tridentate ligand.
  • tetradentate ligands suitable for metal complexes of the present invention may include, but are not limited to: salen derivatives 1, derivatives of salan ligands 2, bis-2-hydroxybenzamido derivatives 3, derivatives of the Trost ligand 4, porphyrin derivatives 5, derivatives of tetrabenzoporphyrin ligands 6, derivatives of corrole ligands 7, phthalocyaninate derivatives 8, and dibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives 9 or 9'.
  • a metal multidentate ligand coordinated with a metal complex may comprise a plurality of discrete ligands.
  • metal complexes include two bidentate ligands.
  • such bidentate ligands may have the structure where R d and R 1 are as defined above.
  • Metal complexes having two such ligands may adopt one of several geometries, and the present disclosure encompasses such variations.
  • metal complexes including two bidentate ligands may have structures selected from the group consisting of:
  • a tetradentate ligand is a salen ligand.
  • a metal complex is a metallosalenate.
  • a metal complex is a cobalt salen complex.
  • a metal complex is a chromium salen complex.
  • a metal complex is an aluminum salen complex.
  • At least one activating moiety is tethered to a carbon atom of a phenyl ring of the salicylaldehy de-derived portions of a salen ligand. In certain embodiments, at least one activating moiety is tethered to a carbon atom of a porphyrin ligand. In certain embodiments, at least one activating moiety is tethered to a pyrrole- carbon atom of a porphyrin ligand. In certain embodiments, at least one activating moiety is tethered to a carbon atom forming the bridge between the pyrrole rings of a porphyrin ligand. In certain embodiments, at least one activating moiety is tethered to one or more carbon atoms of only one phenyl ring of the salicylaldehy de-derived portions of a salen ligand, as shown in formula I:
  • M is a metal atom
  • X is a nucleophile capable of ring opening an epoxide
  • k is an integer from 0-2 inclusive
  • R' represents one or more substituents optionally present on the phenyl rings and each R' is independently selected from the group consisting of: halogen, -NO 2 , -CN, -SR y , -S(O)R y , -S(O) 2 R y , -NR y C(O)R y , -OC(O)R y , -CO 2 R y , -NCO, -N 3 , -OR 7 , -OC(O)N(R y ) 2 , -N(R y ) 2 , -NR y C(O)R y , -NR y C(O)OR y ; or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic
  • R y is -H, or an optionally substituted radical selected from the group consisting of Ci- 6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10- membered aryl;
  • activating moieties where is a covalent linker containing one or more atoms selected from the group consisting of C, O, N, S, and Si; Z is a activating functional group and m is an integer from 1 to 4 indicating the number of individual activating functional groups present in each activating moiety.
  • both salicylaldehyde-derived portions of a salen ligand bear one or more activating moieties:
  • provided metal complexes comprise a moiety that has the structure:
  • M is a metal atom
  • R la , R la' , R 2a , R 2a' , R 3a , and R 3a' are independently a (Z) m group, hydrogen, halogen, -OR, -NR 2 , -SR, -CN, -NO 2 , -SO 2 R, -SOR, -SO 2 NR 2 ; -CNO, -NRSO 2 R, -NCO, -N 3 , -SiR 3 ; or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3
  • any of [R 2a' and R 3a' ], [R 2a and R 3a ], [R la and R 2a ], and [R la' and R 2a' ] may optionally be taken together with the carbon atoms to which they are attached to form one or more rings which may in turn be substituted with one or more
  • R 4a is selected from the group consisting of:
  • R c at each occurrence is independently a Z group, hydrogen, halogen,
  • X is a nucleophile capable of ring opening an epoxide
  • At least one of [R 2a and R 3a ] and [R 2a and R 3a ] are taken together to form a ring. In some embodiments, both [R 2a and R 3a ] and [R 2a and R 3a ] are taken together to form rings. In some embodiments, the rings formed by [R 2a and R 3a ] and [R 2a and R 3a ] are substituted phenyl rings. In certain embodiments, one or more of R la , R la , R 2a , R 2a , R 3a , and R 3a' are independently a Z group.
  • a moiety has a structure selected from the group consisting of:
  • M is a metal atom
  • R 4a , R 4a' , R 5a , R 5a' , R 6a , R 6a' , R 7a , and R 7a' are each independently a — ⁇ w z group, hydrogen, halogen, -OR, -NR 2 , -SR, -CN, -NO 2 , -SO 2 R, -SOR, -SO 2 NR 2 ; -CNO, -NRSO 2 R, -NCO, -N 3 , -SiR 3 ; or an optionally substituted radical selected from the group consisting of C 1--20 aliphatic; C 1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-
  • M is Co.
  • R la , R la' , R 4a , R 4a' , R 6a , and R 6a' are each -H.
  • R 5a , R 5a , R 7a and R 7a are each optionally substituted C 1 -C 12 aliphatic.
  • R 4a , R 4a' , R 5a , R 5a' , R 6a , R 6a' , R 7a , and R 7a' are each independently selected from the group consisting of: -H, -SiR 3 ; methyl, ethyl, n-propyl, /-propyl, n-butyl, sec -butyl, /-butyl, isoamyl, /-amyl, thexyl, and trityl.
  • R la , R la , R 4a , R 4a , R 6a , and R 6a' are each -H.
  • R 7a is selected from the group consisting of -H; methyl; ethyl; n-propyl; /-propyl; n-butyl; sec-butyl; /-butyl; isoamyl; /-amyl; thexyl; and trityl.
  • R 5a and R 7a are independently selected from the group consisting of -H; methyl; ethyl; n-propyl; /-propyl; n-butyl; sec-butyl; /-butyl; isoamyl; /-amyl; thexyl; and trityl.
  • one or more of R 5a , R 5a , R 7a and R 7a' is a — group.
  • R 5a and R 5a' are a Z group.
  • a moiety has a structure selected from the group consisting of:
  • At least one of the phenyl rings comprising a salicylaldehy de-derived portion of a catalyst is independently selected from the group consisting of:
  • ⁇ (Z) m represents one or more independently-defined activating moieties which may be bonded to any one or more unsubstituted positions of a salicylaldehyde-derived phenyl ring.
  • activating moiety tethered to the position ortho to a metal-bound oxygen substituent of one or both of the salicylaldehyde-derived phenyl rings of a salen ligand as in formulae 1Ha and 1Hb:
  • R oa are each independently a - Z group, hydrogen, halogen, -OR, -NR 2 , -SR, -CN, -NO 2 , -SO 2 R, -SOR, -SO 2 NR 2 ; -CNO, -NRSO 2 R, -NCO, -N 3 , -SiR 3 ; or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic
  • R 4a , R 4a , R 6a , and R 6a are each hydrogen, and R 5a , R 5a are, independently, optionally substituted C 1 -C 20 aliphatic.
  • At least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:
  • an activating moiety tethered to the position para to the phenolic oxygen of one or both of a salicylaldehy de-derived phenyl rings of the salen ligand as in structures IVa and IVb:
  • M, X, k, R', R 4a , R 4a' , R 6a , R 6a' , R 7a , R 7a' , * , and (Z) m are as defined above.
  • R 4a , R 4a , R 6a , and R 6a are hydrogen, and each R 7a , R 7a is, independently, optionally substituted C 1 -C 20 aliphatic.
  • At least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:
  • activating moiety tethered to the position para to the imine substituent of one or both of the salicylaldehy de-derived phenyl rings of a salen ligand as in formulae Va or Vb:
  • R 4a is h yyddrrooggeenn,, aanndd eeaacchh RR 55a , R 5a , R 7a , R 7a is, independently, hydrogen or optionally substituted C 1 -C 20 aliphatic.
  • At least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:
  • an activating moiety tethered to the position ortho to the imine substituent of one or both of the salicylaldehy de-derived phenyl rings of a salen ligand as in formulae Via and VIb: , where X, k,
  • each R 6a and R 6a is hydrogen
  • each R 5a , R 5a , R 7a , and R 7a is, independently, hydrogen or optionally substituted C 1 -C 20 aliphatic.
  • At least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:
  • each R i 6a a , R 6a , R 4a , and R 4a is, independently, hydrogen or optionally substituted C 1 -C 20 aliphatic.
  • R 6a' , R 4a , and R 4a' is hydrogen.
  • activating moieties tethered to the positions ortho and para to the imine substituent of one or both of the salicylaldehy de-derived phenyl rings of a salen ligand as in formulae Villa and VIIIb: or
  • each R 5a , R 5a , R 7a , and R 7a is, independently, optionally, hydrogen or substituted C 1 -C 20 aliphatic.
  • At least one of the phenyl rings comprising the salicylaldehy de-derived portion of a catalyst is independently selected from the group consisting of:
  • M, X, k, R 4a , R 4a' , R 5a , R 5a' , R 6a , R 6a' , R 7a , R 7a' , , and (Z) m are as defined above with the proviso that the atom of the activating moiety attached to the salen ligand is a carbon atom.
  • each R 4a , R 4a' , R 6a , and R 6a' is hydrogen
  • each R 5a , R 5a' , R 7a , and R 7a' is, independently, hydrogen or optionally substituted C 1 -C 20 aliphatic.
  • metal complexes of structures IXa or IXb above, at least one of the phenyl rings comprising a salicylaldehy de-derived portion of a catalyst is independently selected from the group consisting of:
  • the two phenyl rings derived from salicylaldehyde in the core salen structures need not be the same.
  • a catalyst may have an activating moiety attached to different positions on each of the two rings, and such compounds are specifically encompassed within the scope of the present invention.
  • activating moieties can be present on multiple parts of the ligand, for instance activating moieties can be present on the diamine bridge and on one or both phenyl rings in the same catalyst.
  • the salen ligand cores of catalysts Ia through IXb above are selected from the group shown below wherein any available position may be independently substituted with one or more R-groups or one or more activating moieties as described above.
  • At least one activating moiety is tethered to the diamine-derived portion of the salen ligand, as shown in formula X:
  • salen ligands of formula X are selected from an optionally substituted moiety consisting of:
  • the diamine bridge of catalysts of formula Xa an optionally substituted moiety selected from the group consisting of:
  • metallosalenate complexes of the present invention include, but are not limited to those in Table 1 below:
  • M is Co-X, where X is as defined above. In certain embodiments, for complexes of Table 1, M is Co-OC(O)CFs. In certain embodiments, for complexes of Table 1, M is Co-OAc. In certain embodiments, for complexes of Table 1, M is Co-OC(O)CeF 5 . In certain embodiments, for complexes of Table 1, M is C0-N3. In certain embodiments, for complexes of Table
  • M is Co-Cl. In certain embodiments, for complexes of Table 1, M is Co-nitrophenoxy. In certain embodiments, for complexes of Table 1, M is Co-dinitrophenoxy.
  • M is Cr-X, where X is as defined above.
  • a tetradentate ligand is a porphyrin ligand.
  • a metal complex is a cobalt porphyrin complex.
  • a metal complex is a chromium porphyrin complex.
  • a metal complex is an aluminum porphyrin complex.
  • porphyrin containing metal complexes of the present invention include, but are not limited to:
  • a multidentate ligand is an optionally substituted tetrabenzoporphyrin. Suitable examples include, but are not limited to:
  • M is aluminum. In certain embodiments of porphyrin and phthalocyanine -based complexes described herein, M is cobalt. In certain embodiments of porphyrin and phthalocyanine-based complexes described herein, M is manganese.
  • porphyrin complexes of the present invention include, but are not limited to those in Table 2 below:
  • M is Co-X, where X is as defined above. In certain embodiments, for complexes of Table 2, M is Co-OC(O)CF 3 . In certain embodiments, for complexes of Table 2, M is Co-OAc. In certain embodiments, for complexes of Table 1, M is Co-OC(O)C 6 F 5 . In certain embodiments, for complexes of Table 2, M is C0-N3. In certain embodiments, for complexes of Table
  • M is Co-C1. In certain embodiments, for complexes of Table 2, M is Co-nitrophenoxy. In certain embodiments, for complexes of Table 2, M is Co-dinitrophenoxy.
  • M is Al-X, where X is as defined above. In certain embodiments, for complexes of Table 2, M is Cr-X, where X is as defined above.
  • porphyrin complexes of the present invention are synthesized as shown in the following schemes:
  • the present disclosure provides methods of polymerization comprising contacting an epoxide with carbon dioxide in the presence of a provided metal complex to form a polycarbonate.
  • the present invention provides a method of polymerization, the method comprising:
  • R a is hydrogen or an optionally substituted radical selected from the group consisting of C 1- 3o aliphatic; C 1- 3o heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and
  • each of R b , R c , and R d is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1-12 aliphatic; C 1-12 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
  • any of (R a and R c ), (R c and R d ), and (R a and R b ) can be taken together with intervening atoms to form one or more optionally substituted rings; ontacting the epoxide and carbon dioxide in the presence of a metal complex as described herein to provide a polymer having a formula selected from the group consisting of:
  • a provided polymer has a formula:
  • a provided polymer has a
  • carbon dioxide is optional
  • R b , R c , and R d are each hydrogen.
  • R a is optionally substituted C 1- i2 aliphatic.
  • R a is optionally substituted C 1- i2 heteroaliphatic .
  • the epoxide is ethylene oxide, propylene oxide, or cyclohexene oxide.
  • one of R a , R b , R c , and R d is hydrogen. In certain embodiments, two of R a , R b , R c , and R d are hydrogen. In certain embodiments, three of R a' , R b' , R c' , and R d' are hydrogen. In certain embodiments, R a is hydrogen. In certain embodiments, R b is hydrogen. In certain embodiments, R c is hydrogen. In certain embodiments, R d is hydrogen.
  • R a , R b , R c , and R d are each independently an optionally substituted C 1- 3o aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted C 1--20 aliphatic group. In certain embodiments,
  • R a , R b , R c , and R d are each independently an optionally substituted C 1-12 aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted C 1-8 aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted C3-8 aliphatic group. In certain embodiments, R a ,
  • R b , R c , and R d are each independently an optionally substituted C 3-12 aliphatic group.
  • R a is an optionally substituted C 1-3 o aliphatic group.
  • R b is an optionally substituted C 1- 3o aliphatic group.
  • R c is an optionally substituted C 1- 3o aliphatic group.
  • R d is an optionally substituted C 1- 3o aliphatic group.
  • an R a and an R b attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 3-8- membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.
  • an R a and an R b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12- membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings.
  • an R a and an R b attached to the same carbon are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an R a and an R b attached to the same carbon are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an R a and an R b attached to the same carbon are taken together to form an optionally substituted 5-7-membered carbocyclic ring.
  • an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.
  • an R b and an R c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12- membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings.
  • an R b and an R c attached to adjacent carbons are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an R b and an R c attached to adjacent carbons are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an R b and an R c attached to adjacent carbons are taken together to form an optionally substituted 5-7-membered carbocyclic ring.
  • the polymer comprises a copolymer of two different repeating units where R a , R b , and R c of the two different repeating units are not all the same.
  • a polymer comprises a copolymer of three or more different repeating units wherein R a , R b , and R c of each of the different repeating units are not all the same as R a , R b , and R c of any of the other different repeating units.
  • a polymer is a random copolymer.
  • a polymer is a tapered copolymer.
  • a polymer contains a metal complex as described herein. In some embodiments, a polymer comprises residue of a metal complex as described herein. In some embodiments, a polymer comprises a salt of an organic cation and X, wherein X is a nucleophile or counterion. In some embodiments, X is 2,4- dinitrophenolate anion.
  • R a is optionally substituted C 1-12 aliphatic. In some embodiments, R a is optionally substituted C 1-12 heteroaliphatic. In some embodiments, R a is optionally substituted phenyl. In some embodiments, R a is optionally substituted 8- to 10-membered aryl. In some embodiments, R a is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R a is optionally substituted 3- to 7-membered heterocyclic . In certain embodiments, R a is selected from methyl, ethyl, propyl, butyl, vinyl,
  • R a is methyl. In certain embodiments, R a is ethyl. In certain embodiments, R a is propyl. In certain embodiments, R a is butyl. In certain embodiments, R a is vinyl. In certain embodiments, R a is allyl. In certain embodiments, R a is phenyl. In certain embodiments, R a is trifluoromethyl. In certain embodiments,
  • R a is . In certain embodiments, R a is . In certain embodiments,
  • R a is . In certain embodiments, R a' is In certain embodiments, R a' is . In certain
  • R a is
  • R b is hydrogen. In some embodiments, R b is optionally substituted C 1-12 aliphatic. In some embodiments, R b is optionally substituted C 1-12 heteroaliphatic. In some embodiments, R b is optionally substituted phenyl. In some embodiments, R b is optionally substituted 8- to 10-membered aryl. In some embodiments, R b is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R b is optionally substituted 3- to 7-membered heterocyclic .
  • R c is hydrogen. In some embodiments, R c is optionally substituted C 1-12 aliphatic. In some embodiments, R c is optionally substituted C 1-12 heteroaliphatic. In some embodiments, R c is optionally substituted phenyl. In some embodiments, R c is optionally substituted 8- to 10-membered aryl. In some embodiments, R c is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R c is optionally substituted 3- to 7-membered heterocyclic .
  • R a and R c are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 .
  • R b and R c are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 - C 14 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted C 8 -C 10 aryl, and optionally substituted 5- to 10- membered heteroaryl.
  • R a and R b are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3-
  • C 14 carbocycle optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted C 8 -C 10 aryl, and optionally substituted 5- to 10- membered heteroaryl.
  • the invention includes methods for synthesizing polyethers from epoxides. Suitable methods of performing these reactions are disclosed in US Patent No. 7,399,822, the entire contents of which are hereby incorporated herein by reference.
  • the invention includes methods for synthesizing cyclic carbonates from carbon dioxide and epoxides using catalysts described above, suitable methods of performing this reaction are disclosed in US Patent No. 6,870,004 which is incorporated herein by reference.
  • Example 3 describes the synthesis of a catalyst s where M is
  • Co(III) is salcy, is , Z is a P-linked phosphorimine moiety , and m is 1, wherein there are one or two groups present (Scheme E4 and E3, respectively).
  • triol E3-a is protected as a ketal to afford monohydric alcohol E3-b, this compound is then alkylated with bromide E3-c to afford benzyl ether E3-d.
  • Deprotection and oxidation of the other benzylic alcohol affords salicylaldehyde E3-e which is condensed with cyclohexanediamine as described above to give ligand E3- f.
  • the phosphorimine nitrogen is then quaternized and the metal complex formed as before to provide catalyst E3-h.
  • the metal is first inserted and then quarternization is performed.
  • Example 4 describes the synthesis of catalysts where M is Co(III), is salcy, is , Z is a l-[4-dimethylamino-pyridinium] or 1-[N- methylimidazolium], and m is 1, wherein there are one or two TM groups present (Scheme E5 and E6, respectively).
  • Z' N,N-dimethyla or N-methyl im
  • Scheme E4 shows the synthesis of compounds CS-6 and CS-7.
  • trans- 1 ,2-Diaminocycloh.exane 2.0 mol
  • benzyl chloride CS-4 1.0 mol
  • the reaction is stirred and heated to reflux for 3 h, then cooled to rt and diluted with water. This mixture is cooled overnight in the freezer and solids are collected by filtration to afford dichloride CS-5.
  • the dichloride CS-5 (1.0 mol) is reacted with N,N-Dimethylamino pyridine (2.0 mol) or N- methyl imidazole in acetonitrile.
  • the reactions are heated at 80 °C for 18 h and then the solvent is removed in vacuo to provide the respective ammonium salts. These salts are metallated and oxidized as described previously to provide catalysts CS-6 and CS-7.
  • Example 5 Example 5
  • Example 5 describes the synthesis of catalysts where M is Co(III), is salcy, is , Z is a l-[N-methylimidazolium] (CS-8), or dimethylamino (CS-9) and m is 1, wherein there are two groups present (Scheme E5 and E6, respectively).
  • Scheme E5 shows the synthesis of compounds CS-8 and CS-9 using conditions similar to those described above.
  • Synthesis of CS-8 The known compound l-(2- methylaminoethyl)-3-methylimidazole (2.0 mol) is combined with CS-5 (1.0 mol) in acetonitrile. The reaction is heated to 80 °C for 18 h and then the solvent is removed in vacuo, metallation with Co(OAc) 2 and oxidation in TFA are then performed as described above to afford catalyst CS-8.
  • Synthesis of CS-9 N 5 N 5 N '-Trimethyl-1 ,2-ethanediamine (4.0 mol) is combined with CS-5 (1.0 mol) in acetonitrile.
  • Example 6 and Scheme E6 describe the synthesis of catalysts where M is Co(III), is salcy, is , Z is dibutylamino and m is 1, wherein there are two groups present.
  • Example 7 and Scheme E7 describe the synthesis of catalysts where M is Co(III), is salcy, includes two groups taken together to form a ring including the Z group, Z is 3-[N-methylpyridinium] and m is 1, wherein there is one (Z) m group present.
  • Example 8 and Scheme E8 describe the synthesis of catalysts where M is Co(III), , Z is l-[4-t-butylpyridinium], and m is 2, wherein there are two (Z) m groups present.
  • Example 9 and Scheme E9 describe the synthesis of catalysts where M is Co(III), is salcy, is , Z is N,N-bis-(3-dimethylaminopropyl)amino (AC-4), tetramethyl guanidino (AC-5), N-linked morpholino (AC-6), or N-linked piperidino (AC- 14), and m is 2, wherein there are two (Z) m groups present.
  • provided catalysts and/or methods for the preparation of polycarbonate are characterized by one or more of the following: retaining high catalytic activity at low catalyst concentration; reaction conditions that are relatively mild; high catalytic activity with high selectivity for polymer product; alternate structure in the polycarbonate product higher than 97% with relatively narrow distribution of molecular weight; retaining high catalytic activity for copolymerization of carbon dioxide and epoxides at higher reaction temperatures (e.g., above 50 °C, above 75 °C, or above 100 °C); and catalysts that can be used to catalyze the polymerization of carbon dioxide with two or more alkylene oxides for the synthesis of polycarbonate polymer.
  • the remaining alkylene oxide was collected in -20 °C cold trap and a certain amount of mixture of methanol/chloroform was added to dissolve the high polymer. Then a large amount of diethyl ether was added to precipitate the polycarbonate. The precipitate was filtered and washed several times with diethyl ether and dried in vacuum to constant weight to afford 27 grams of polycarbonate as a white solid.
  • the average molecular weight of the polymer was determined by gel permeation chromatography to be 101,000 g/mol with a molecular weight distribution of 1.24.
  • a Varian INOVA-400MHz Nuclear Magnetic Resonance spectrometer was used to determine its 1 H-NMR and the result showed that the alternate structure is over 99%.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the molar ratio of catalyst to propylene oxide was changed from 1 :10000 to 1 :50000 (0.02 mmole of catalyst and 1 mole of propylene oxide were used).
  • the reaction was carried out at 25 °C for 24 hours to afford 21 grams of poly(propylene carbonate) with a molecular weight of 223,000 g/mol and a molecular weight distribution of 1.29.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the molar ratio of catalyst to propylene oxide was changed from 1 :10000 to 1 :200000 (0.008 mmole of catalyst and 1.6 mole of propylene oxide were used).
  • the reaction was carried out at 50 °C for 10 hours to afford 19 grams of poly(propylene carbonate) with a molecular weight of 318,000 g/mol and a molecular weight distribution of 1.37.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the molar ratio of catalyst to propylene oxide was changed from 1 :10000 to 1 :2000 (0.5 mmole of catalyst and 1 mole of propylene oxide were used).
  • the reaction was carried out at 25 °C for 3 hours to afford 48 grams of poly(propylene carbonate) with a molecular weight of 52,800 g/mol and a molecular weight distribution of 1.30.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the reaction temperature was changed from 25 °C to 100 °C and the reaction was carried out for 0.5 hours to afford 34 grams of poly(propylene carbonate) with a molecular weight of 112,400 g/mol and a molecular weight distribution of 1.38.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the reaction temperature was changed from 25 °C to 10 °C and the reaction was carried out for 10 hours to afford 18 grams of poly(propylene carbonate) with a molecular weight of 914,000 g/mol and a molecular weight distribution of 1.38.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the propylene oxide was replaced with 1,2-butylene oxide.
  • the reaction was carried out at 25 °C for 6 hours to afford 31 grams of poly(butylene carbonate) with a molecular weight of 127,000 g/mol and a molecular weight distribution of 1.21.
  • the polymer formed contained more than
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the propylene oxide was replaced with 1,2-octylene oxide.
  • the reaction was carried out at 25 °C for 10 hours to afford 34 grams of poly(octylene carbonate) with a molecular weight of 109,000 g/mol and a molecular weight distribution of 1.38.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the propylene oxide was replaced with a mixture of propylene oxide and cyclohexylene oxide (the molar ratio of the catalyst to propylene oxide and cyclohexylene oxide was 1 : 5000: 5000).
  • the reaction was carried out at 50 °C for 6 hours to afford 59 grams of poly(propylene-co-cylcohexene carbonate) with a molecular weight of 187,000 g/mol and a molecular weight distribution of 1.29.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the axial anion in the cobalt complex I-a was changed from nitrate radical to acetate moiety.
  • the reaction was carried out at 25 °C for 6 hours to afford 34 grams of poly(propylene carbonate) with a molecular weight of 95,000 g/mol and a molecular weight distribution of 1.28.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the diamine skeleton in the cobalt complex I-a was changed from cyclohexane diamine to ethylene diamine.
  • the reaction was carried out at 25 °C for 6 hours to afford 29 grams of poly(propylene carbonate) with a molecular weight of 112,000 g/mol and a molecular weight distribution of 1.20.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the diamine skeleton in the cobalt complex I-a was changed from cyclohexane diamine to o-phenylene diamine.
  • the reaction was carried out at 25 °C for 6 hours to afford 25 grams of poly (propylene carbonate) with a molecular weight of 92,000 g/mol and a molecular weight distribution of 1.15.
  • the polymer formed contained more than 99% carbonate linkages.
  • the average molecular weight of the polymer was determined by gel permeation chromatography to be 83,000 g/mol with a molecular weight distribution of 1.19.
  • the polymer formed contained more than 99% carbonate linkages.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the pressure was changed from 2.0 MPa to 0.1 MPa.
  • the reaction was carried out at 25 °C for 10 hours to afford 25 grams of poly(propylene carbonate) with a molecular weight of 100,400 g/mol and a molecular weight distribution of 1.17.
  • the polymer formed contained more than 99% carbonate linkages.
  • Example 10 The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the pressure was changed from 2.0 MPa to 6.0 MPa.
  • the reaction was carried out at 25 °C for 6 hours to afford 29 grams of poly(propylene carbonate) with a molecular weight of 125,000 g/mol and a molecular weight distribution of 1.25.
  • the polymer formed contained more than 99% carbonate linkages.

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Abstract

The present invention provides unimolecular metal complexes having increased activity in the copolymerization of carbon dioxide and epoxides. Also provided are methods of using such metal complexes in the synthesis of polymers. According to one aspect, the present invention provides metal complexes comprising an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to the active metal center of the complex.

Description

CATALYSTS AND METHODS FOR POLYMER SYNTHESIS
Priority Claim
This application claims priority to United States Provisional Patent Application Serial No. 61/091,013, filed August 22, 2008; United States Provisional Patent Application Serial No. 61/096,313, filed September 11, 2008 and United States
Provisional Patent Application Serial No. 61/098,739, filed September 19, 2008. The entire contents of each of these priority applications are incorporated herein by reference.
Background
Catalysts capable of effecting the copolymerization of epoxides and carbon dioxide to form aliphatic polycarbonates (APCs) have been known in the art since the 1960s. The early catalysts were based on heterogeneous zinc compounds and suffered from low reactivity, a lack of selectivity for polymer formation vs. cyclic carbonate formation, and a tendency to produce polycarbonates contaminated with ether linkages.
Improved catalysts based on transition metals have been discovered over the past decade or so. These newer catalysts have increased reactivity and improved selectivity.
Nevertheless, even using highly active catalysts such as those disclosed in US patent 7,304,172, the reaction times required to make high molecular weight polymer are typically quite long. In addition, the best-performing catalysts disclosed in the ' 172 patent require the addition of a separate co-catalyst to achieve optimum activity.
Attempts to address these shortcomings have been made. Catalysts described by
Nozaki and co-workers (Angew. Chem. Int. Ed. 2006, 45_, 7274 -7277) tether an amine co-catalyst to a ligand of the catalyst. These next-generation catalytic systems suffer from lengthy and complicated syntheses and undesirable induction times prior to onset of polymerization. There remains a need for catalysts that have increased activity that will further reduce the polymerization time required to produce high molecular weight APCs. Summary
The present invention provides, among other things, unimolecular catalyst systems having activity in the copolymerization of carbon dioxide and epoxides and methods of using the same. In some embodiments, the present invention provides metal complexes having an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to an active metal center of a metal complex.
In certain embodiments, the present invention provides unimolecular metal complexes and methods for using the same in the copolymerization of carbon dioxide and epoxides. In some embodiments, provided metal complexes have the structure:
Figure imgf000003_0001
wherein:
M is a metal atom;
Figure imgf000003_0002
comprises a multidentate ligand; (Z)m represents one or more activating moieties attached to the multidentate ligand, where
Figure imgf000003_0003
is a linker moiety covalently coupled to the ligand, each Z is an activating functional group; and m is an integer from 1 to 4 representing the number of Z groups present on an individual linker moiety.
In some embodiments, tethered activating functional groups (Z) are neutral nitrogen-containing moieties. In certain embodiments, neutral nitrogen-containing moieties are selected from the group consisting of:
Figure imgf000004_0001
or a combination of two or more of these,
wherein:
each occurrence of R1, and R2 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein R1 and R2 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms;
each occurrence of R5 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7- 14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly eye lie saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein an R5 group can be taken with an R1 or R2 group to form one or more optionally substituted rings; and
each occurrence of R7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C1--20 acyl; C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In some embodiments, tethered activating functional groups (Z) are cationic moieties. In certain embodiments, cationic moieties are selected from the group consisting of:
Figure imgf000006_0001
Figure imgf000006_0003
Figure imgf000006_0004
or a combination of two or more of these,
Figure imgf000006_0002
wherein:
each occurrence of R1, R2, and R3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more R1, R2, and R3 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms;
R4 is hydrogen or -OR7;
R4 is hydrogen, hydroxyl, or optionally substituted C1--20 aliphatic;
each occurrence of R5 and R6 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein R5 and R6 can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, and an R5 or R6 group can be taken with an R1 or R2 group to form one or more optionally substituted rings;
each occurrence of R7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C1--20 acyl; C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
each occurrence of R8, R9, and R10 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more R8, R9 and R10 groups can be taken together with intervening atoms to form one or more optionally substituted rings;
each occurance of R11 is independently selected from the group consisting of: halogen, -NO2, -CN, -SRy, -S(O)Ry, -S(O)2Ry, -NRyC(O)Ry, -OC(O)Ry, -CO2Ry, -NCO, -N3, -OR7, -OC(O)N(Ry)2, -N(Ry)2, -NRyC(O)Ry, -NRyC(O)ORy; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; where each occurrence of Ry is independently -H, or an optionally substituted radical selected from the group consisting of Ci-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10- membered aryl, and where two or more adjacent R11 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;
X- is any anion, and
Ring A is an optionally substituted, 5- to 10-membered heteroaryl group.
In some embodiments, an activating functional group (Z) is a phosphorous- containing functional group.
In certain embodiments, a phosphorous-containing functional group is chosen from the group consisting of: phosphines (-PRy2); Phosphine oxides -P(O)Ry2; phosphinites P(OR7)Ry 2; phosphonites P(OR7)2Ry; phosphites P(OR7)3; phosphinates OP(OR7)Ry 2; phosphonates; OP(OR7)2Ry; phosphates -OP(OR7)3; phosponium salts ([-PRy 3]+) where the phosphorous-containing functional group may be linked to a metal complex through any available position (e.g. direct linkage via the phosphorous atom, or in some cases via an oxygen atom).
In certain embodiments, a phosphorous-containing functional group is chosen from the group consisting of:
Figure imgf000009_0001
or a combination of two or more of these
wherein R1 and R2, are as defined above; and each R7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C1--20 acyl; C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and where two R7 groups can be taken together with intervening atoms to form an optionally substituted ring optionally containing one or more heteroatoms, and an R7 group can be taken with an R1 or R2 group to an optionally substituted ring;
In some embodiments, phosphorous containing functional groups include those disclosed in The Chemistry of Organophosphorus Compounds. Volume 4. Ter- and Quinquevalent Phosphorus Acids and their Derivatives. The Chemistry of Functional Group Series Edited by Frank R. Hartley (Cranfield University, Cranfield, U.K.). Wiley: New York. 1996. ISBN 0-471-95706-2, the entirety of which is hereby incorporated herein by reference.
In certain embodiments, a phosphorous-containing functional group has the structure , wherein:
Figure imgf000010_0001
X is -O-, -N=, or -NRZ-,
b is 1 or 0,
each of R6, R7 and R8 are independently present or absent and, if present, are independently selected from the group consisting of optionally substituted C1-C20 aliphatic, optionally substituted C6-C14 aryl, optionally substituted 3- to 14- membered heterocyclic, optionally substituted 5- to 14-membered heteroaryl, halogen, =0, -ORZ, =NRZ, and N(RZ)2 where Rz is hydrogen, or an optionally substituted C1-C20 aliphatic, optionally substituted 6- to 14-membered aryl, optionally substituted 3- to 14-membered heterocyclic, or optionally substituted 5- to 14-membered heteroaryl,
Q is any anion, and
n is an integer between 1 and 4.
In some embodiments, the present disclosure encompasses methods for the copolymerization of epoxides and carbon dioxide, such methods comprising contacting one or more epoxides with a catalyst described above in the presence of carbon dioxide.
In some embodiments, the present disclosure encompasses methods for the formation of cyclic carbonates from epoxides and carbon dioxide, such methods comprising contacting one or more epoxides with a catalyst described above in the presence of carbon dioxide.
In some embodiments, the present disclosure encompasses methods for the formation of poly ethers, such methods comprising contacting one or more epoxides with a catalyst described above.
Definitions Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic
Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March 's Advanced Organic Chemistry, 5th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3rd Edition, Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.
Certain compounds of the present invention can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers. Thus, inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers. In certain embodiments, the compounds of the invention are enantiopure compounds. In certain embodiments, mixtures of enantiomers or diastereomers are provided.
Furthermore, certain compounds, as described herein may have one or more double bonds that can exist as either a Z or E isomer, unless otherwise indicated. The invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic mixtures of enantiomers. In addition to the above-mentioned compounds per se, this invention also encompasses compositions comprising one or more compounds.
As used herein, the term "isomers" includes any and all geometric isomers and stereoisomers. For example, "isomers" include cis- and trans-isomcrs, E- and Z- isomers, R- and ^-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention. For instance, a compound may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as "stereochemically enriched."
Where a particular enantiomer is preferred, it may, in some embodiments be provided substantially free of the opposite enantiomer, and may also be referred to as "optically enriched." "Optically enriched," as used herein, means that the compound is made up of a significantly greater proportion of one enantiomer. In certain embodiments the compound is made up of at least about 90% by weight of an enantiomer. In some embodiments the compound is made up of at least about 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9% by weight of an enantiomer. In some embodiments the enantiomeric excess of provided compounds is at least about 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9%. In some embodiments, enantiomers may be isolated from racemic mixtures by any method known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts or prepared by asymmetric syntheses. See, for example, Jacques, et al.,
Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981); Wilen, S.H., et al., Tetrahedron 33:2725 (1977); Eliel, E.L. Stereochemistry of Carbon Compounds (McGraw-Hill, NY, 1962); Wilen, S. H. Tables of Resolving Agents and Optical Resolutions p. 268 (E.L. Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, IN 1972).
The terms "halo" and "halogen" as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodo, -I).
The term "aliphatic" or "aliphatic group", as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-30 carbon atoms. In certain embodiments, aliphatic groups contain 1-12 carbon atoms. In certain embodiments, aliphatic groups contain 1-8 carbon atoms. In certain embodiments, aliphatic groups contain 1-6 carbon atoms. In some embodiments, aliphatic groups contain 1-5 carbon atoms, in some embodiments, aliphatic groups contain 1-4 carbon atoms, in yet other embodiments aliphatic groups contain 1-3 carbon atoms, and in yet other embodiments aliphatic groups contain 1-2 carbon atoms. Suitable aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl. In certain embodiments, the term aliphatic group encompasses aliphatic groups wherein one or more hydrogen atoms are replaced with a halogen atom. In certain embodiments, the term aliphatic group encompasses chlorinated or fluorinated aliphatic groups including perfluorinated compounds.
The term "epoxide", as used herein, refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. Such epoxides may be further optionally substituted as defined herein. In certain embodiments, epoxides comprise a single oxirane moiety. In certain embodiments, epoxides comprise two or more oxirane moieties.
The term "polymer", as used herein, refers to a molecule of high relative molecular mass, the structure of which comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass. In certain embodiments, a polymer is comprised of only one monomer species (e.g., polyethylene oxide). In certain embodiments, a polymer of the present invention is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer of one or more epoxides.
The term "unsaturated", as used herein, means that a moiety has one or more double or triple bonds.
The terms "cycloaliphatic", "carbocycle", or "carbocyclic", used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cyclic aliphatic monocyclic, bicyclic, or polycyclic ring systems, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined above and described herein. Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, and cyclooctadienyl. In some embodiments, the cycloalkyl has 3-6 carbons. The terms "cycloaliphatic", "carbocycle" or "carbocyclic" also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring. In some embodiments, a carbocyclic groups is bicyclic. In some embodiments, a carbocyclic group is tricyclic. In some embodiments, a carbocyclic group is polycyclic.
The term "alkyl," as used herein, refers to saturated, straight- or branched-chain hydrocarbon radicals derived by removal of a single hydrogen atom from an aliphatic moiety. Unless otherwise specified, alkyl groups contain 1-12 carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbon atoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5 carbon atoms, in some embodiments, alkyl groups contain 1-4 carbon atoms, in yet other embodiments alkyl groups contain 1-3 carbon atoms, and in yet other embodiments alkyl groups contain 1-2 carbon atoms. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.
The term "alkenyl," as used herein, denotes a monovalent group derived by the removal of a single hydrogen atom from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond. Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. In certain embodiments, alkenyl groups contain 2-8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2-5 carbon atoms, in some embodiments, alkenyl groups contain 2-4 carbon atoms, in yet other embodiments alkenyl groups contain 2-3 carbon atoms, and in yet other embodiments alkenyl groups contain 2 carbon atoms. Alkenyl groups include, for example, ethenyl, propenyl, allyl, 1,3-butadienyl, butenyl, l-methyl-2-buten-1-yl, allyl, 1,3-butadienyl, allenyl, and the like.
The term "alkynyl," as used herein, refers to a monovalent group derived by the removal of a single hydrogen atom from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond. Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms. In some embodiments, alkynyl groups contain 2-5 carbon atoms, in some embodiments, alkynyl groups contain 2-4 carbon atoms, in yet other embodiments alkynyl groups contain 2-3 carbon atoms, and in yet other embodiments alkynyl groups contain 2 carbon atoms. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.
The term "carbocycle" and "carbocyclic ring" as used herein, refer to monocyclic and polycyclic moieties wherein the rings contain only carbon atoms. Unless otherwise specified, carbocycles may be saturated, partially unsaturated or aromatic, and contain 3 to 20 carbon atoms. Representative carbocyles include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2,l]heptane, norbornene, phenyl, cyclohexene, naphthalene, and spiro[4.5]decane, to name but a few.
The term "aryl" used alone or as part of a larger moiety as in "aralkyl", "aralkoxy", or "aryloxyalkyl", refers to monocyclic and polycyclic ring systems having a total of six to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members. The term "aryl" may be used interchangeably with the term "aryl ring". In certain embodiments of the present invention, "aryl" refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents. Also included within the scope of the term "aryl", as it is used herein, is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like.
The term "heteroaliphatic," as used herein, refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, phosphorus, or boron. In certain embodiments, one to six carbon atoms are independently replaced by one or more of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated or partially unsaturated groups.
The terms "heteroaryl" and "heteroar-", used alone or as part of a larger moiety, e.g., "heteroaralkyl", or "heteroaralkoxy", refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 π electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms. The term
"heteroatom" refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen. Heteroaryl groups include, without limitation, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl and pteridinyl. The terms "heteroaryl" and "heteroar-", as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring. Nonlimiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazin-3(4Η)-one. A heteroaryl group may be mono- or polycyclic. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring", "heteroaryl group", or "heteroaromatic", any of which terms include rings that are optionally substituted. The term "heteroaralkyl" refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.
As used herein, the terms "heterocycle", "heterocyclyl", "heterocyclic radical", and "heterocyclic ring" are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7-14-membered bicyclic heterocyclic moiety that is saturated, partially unsaturated, or aromatic and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above. When used in reference to a ring atom of a heterocycle, the term "nitrogen" includes a substituted nitrogen. As an example, in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or +NR (as in N-substituted pyrrolidinyl).
A heterocyclic ring can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted. Examples of such saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms "heterocycle", "heterocyclyl", "heterocyclyl ring", "heterocyclic group", "heterocyclic moiety", and
"heterocyclic radical", are used interchangeably herein, and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, where the radical or point of attachment is on the heterocyclyl ring. A heterocyclyl group may be mono- or bicyclic. The term "heterocyclylalkyl" refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions independently are optionally substituted.
The term "acyl" as used herein refers to a group having a formula -C(O)R where R is hydrogen or an optionally substituted aliphatic, aryl, or heterocyclic group.
As used herein, the term "partially unsaturated" refers to a ring moiety that includes at least one double or triple bond. The term "partially unsaturated" is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as herein defined.
One of ordinary skill in the art will appreciate that the synthetic methods, as described herein, utilize a variety of protecting groups. By the term "protecting group," as used herein, it is meant that a particular functional moiety, e.g., O, S, or N, is masked or blocked, permitting, if desired, a reaction to be carried out selectively at another reactive site in a multifunctional compound. In preferred embodiments, a protecting group reacts selectively in good yield to give a protected substrate that is stable to the projected reactions; the protecting group is preferably selectively removable by readily available, preferably non-toxic reagents that do not attack the other functional groups; the protecting group forms a separable derivative (more preferably without the generation of new stereogenic centers); and the protecting group will preferably have a minimum of additional functionality to avoid further sites of reaction. As detailed herein, oxygen, sulfur, nitrogen, and carbon protecting groups may be utilized. By way of non- limiting example, hydroxyl protecting groups include methyl, methoxylmethyl (MOM), methylthiomethyl (MTM), t-butylthiomethyl, (phenyldimethylsilyl)methoxymethyl (SMOM), benzyloxymethyl (BOM), p--methoxybenzyloxymethyl (PMBM), (4- methoxyphenoxy)methyl (p-AOM), guaiacolmethyl (GUM), t-butoxymethyl, 4- pentenyloxymethyl (POM), siloxymethyl, 2-methoxyethoxymethyl (MEM), 2,2,2-trichloroethoxymethyl, bis(2-chloroethoxy)methyl, 2-(trimethylsilyl)ethoxymethyl (SEMOR), tetrahydropyranyl (THP), 3-bromotetrahydropyranyl, tetrahydrothiopyranyl, 1-methoxycyclohexyl, 4-methoxytetrahydropyranyl (MTHP), 4- methoxytetrahydrothiopyranyl, 4-methoxytetrahydrothiopyranyl S,S-dioxide, 1 -[(2-chloro-4-methyl)phenyl]-4-methoxypiperidin-4-yl (CTMP), 1 ,4-dioxan-2-yl, tetrahydrofuranyl, tetrahydrothiofuranyl,
2,3,3a,4,5,6,7,7a-octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-yl, 1-ethoxyethyl, 1 -(2-chloroethoxy)ethyl, 1 -methyl- 1 -methoxy ethyl, 1 -methyl- 1 -benzyloxy ethyl, 1 -methyl- 1 -benzyloxy-2-fluoroethyl, 2,2,2-trichloroethyl, 2-trimethylsilylethyl, 2-(phenylselenyl)ethyl, t-butyl, allyl, p-chlorophenyl,p-methoxyphenyl, 2,4- dinitrophenyl, benzyl, p-methoxybenzyl, 3,4-dimethoxybenzyl, o-nitrobenzyl, p-nitrobenzyl, p-halobenzyl, 2,6-dichlorobenzyl,p-cyanobenzyl, p -phenylbenzyl, 2-picolyl, 4-picolyl, 3-methyl-2-picolyl N-oxido, diphenylmethyl, p,p '-dinitrobenzhydryl, 5-dibenzosuberyl, triphenylmethyl, α-naphthyldiphenylmethyl, p-methoxyphenyldiphenylmethyl, di(p-methoxyphenyl)phenylmethyl, tri(p-methoxyphenyl)methyl, 4-(4 ' -bromophenacyloxyphenyl)diphenylmethyl, 4,4 ' ,4 " -tris(4,5-dichlorophthalimidophenyl)methyl,
4,4 ' ,4 " -tris(levulinoyloxyphenyl)methyl, 4,4 ' ,4 " -tris(benzoyloxyphenyl)methyl, 3- (imidazol- 1 -yl)bis(4 ' ,4 " -dimethoxyphenyl)methyl, 1 , 1 -bis(4- methoxyphenyl)-l '-pyrenylmethyl, 9-anthryl, 9-(9-phenyl)xanthenyl, 9-(9-phenyl-10-oxo)anthryl, 1,3-benzodithiolan-2-yl, benzisothiazolyl S,S-dioxido, trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), dimethylisopropylsilyl (IPDMS), diethylisopropylsilyl (DEIPS), dimethylthexylsilyl, t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl (TBDPS), tribenzylsilyl, tri-p-xylylsilyl, triphenylsilyl, diphenylmethylsilyl (DPMS), t-butylmethoxyphenylsilyl (TBMPS), formate, benzoylformate, acetate, chloroacetate, dichloroacetate, trichloroacetate, trifluoroacetate, methoxyacetate, triphenylmethoxyacetate, phenoxyacetate,p-chlorophenoxyacetate, 3- phenylpropionate, 4-oxopentanoate (levulinate), 4,4-(ethylenedithio)pentanoate (levulinoyldithioacetal), pivaloate, adamantoate, crotonate, 4-methoxycrotonate, benzoate, p-phenylbenzoate, 2,4,6-trimethylbenzoate (mesitoate), alkyl methyl carbonate, 9-fluorenylmethyl carbonate (Fmoc), alkyl ethyl carbonate, alkyl 2,2,2-trichloroethyl carbonate (Troc), 2-(trimethylsilyl)ethyl carbonate (TMSEC), 2-(phenylsulfonyl) ethyl carbonate (Psec), 2-(triphenylphosphonio) ethyl carbonate (Peoc), alkyl isobutyl carbonate, alkyl vinyl carbonate alkyl allyl carbonate, alkyl p-nitrophenyl carbonate, alkyl benzyl carbonate, alkyl p-methoxybenzyl carbonate, alkyl 3,4-dimethoxybenzyl carbonate, alkyl o-nitrobenzyl carbonate, alkyl p-nitrobenzyl carbonate, alkyl S-benzyl thiocarbonate, 4-ethoxy-l-napththyl carbonate, methyl dithiocarbonate, 2-iodobenzoate, 4-azidobutyrate, 4-nitro-4-methylpentanoate, o-(dibromomethyl)benzoate,
2-formylbenzenesulfonate, 2-(methylthiomethoxy)ethyl, 4-(methylthiomethoxy)butyrate, 2-(methylthiomethoxymethyl)benzoate, 2,6-dichloro-4-methylphenoxyacetate, 2,6- dichloro-4-( 1 , 1 ,3 ,3-tetramethylbutyl)phenoxyacetate, 2,4- bis( 1 , 1 -dimethylpropyl)phenoxyacetate, chlorodiphenylacetate, isobutyrate, monosuccinoate, (E)-2-methyl-2-butenoate, o-(methoxycarbonyl)benzoate, α-naphthoate, nitrate, alkyl N,Λ/,N',N'-tetramethylphosphorodiamidate, alkyl N-phenylcarbamate, borate, dimethylphosphinothioyl, alkyl 2,4-dinitrophenylsulfenate, sulfate, methanesulfonate (mesylate), benzylsulfonate, and tosylate (Ts). For protecting 1,2- or 1,3-diols, the protecting groups include methylene acetal, ethylidene acetal, 1-t-butylethylidene ketal, 1-phenylethylidene ketal, (4-methoxyphenyl)ethylidene acetal,
2,2,2-trichloroethylidene acetal, acetonide, cyclopentylidene ketal, cyclohexylidene ketal, cycloheptylidene ketal, benzylidene acetal, p-methoxybenzylidene acetal, 2,4- dimethoxybenzylidene ketal, 3,4-dimethoxybenzylidene acetal, 2-nitrobenzylidene acetal, methoxymethylene acetal, ethoxymethylene acetal, dimethoxymethylene ortho ester, 1-methoxy ethylidene ortho ester, 1-ethoxyethylidine ortho ester,
1 ,2-dimethoxyethylidene ortho ester, α-methoxybenzylidene ortho ester, 1 -(Λ/,Λ/-dimethylamino)ethylidene derivative, α-(Λ/,N'-dimethylamino)benzylidene derivative, 2-oxacyclopentylidene ortho ester, di-t-butylsilylene group (DTBS), 1,3- (1,1,3,3-tetraisopropyldisiloxanylidene) derivative (TIPDS), tetra-t-butoxydisiloxane-1,3- diylidene derivative (TBDS), cyclic carbonates, cyclic boronates, ethyl boronate, and phenyl boronate. Amino-protecting groups include methyl carbamate, ethyl carbamante, 9-fluorenylmethyl carbamate (Fmoc), 9-(2-sulfo)fluorenylmethyl carbamate, 9-(2,7-dibromo)fluoroenylmethyl carbamate, 2,7-di-t-butyl-[9-( 10,10-dioxo- 10,10,10,10-tetrahydrothioxanthyl)]methyl carbamate (DBD-Tmoc), 4-methoxyphenacyl carbamate (Phenoc), 2,2,2-trichloroethyl carbamate (Troc), 2-trimethylsilylethyl carbamate (Teoc), 2-phenylethyl carbamate (hZ), l-(l-adamantyl)-l-methylethyl carbamate (Adpoc), l,l-dimethyl-2-haloethyl carbamate, l,l-dimethyl-2,2-dibromoethyl carbamate (DB-t-BOC), l,l-dimethyl-2,2,2-trichloroethyl carbamate (TCBOC), 1 -methyl- l-(4-biphenylyl)ethyl carbamate (Bpoc), l-(3,5- di-£-butylphenyl)-1-methylethyl carbamate (t-Bumeoc), 2-(2'- and 4'-pyridyl)ethyl carbamate (Pyoc), 2-(/V, N-dicyclohexylcarboxamido)ethyl carbamate, t-butyl carbamate (BOC), 1-adamantyl carbamate (Adoc), vinyl carbamate (Voc), allyl carbamate (Alloc),
1-isopropylallyl carbamate (Ipaoc), cinnamyl carbamate (Coc), 4-nitrocinnamyl carbamate (Noc), 8-quinolyl carbamate, N-hydroxypiperidinyl carbamate, alkyldithio carbamate, benzyl carbamate (Cbz), p-methoxybenzyl carbamate (Moz), p-nitobenzyl carbamate, p-bromobenzyl carbamate, p-chlorobenzyl carbamate, 2,4-dichlorobenzyl carbamate, 4-methylsulfinylbenzyl carbamate (Msz), 9-anthrylmethyl carbamate, diphenylmethyl carbamate, 2-methylthioethyl carbamate, 2-methylsulfonylethyl carbamate, 2-(p-toluenesulfonyl)ethyl carbamate, [2-(1,3-dithianyl)]methyl carbamate (Dmoc), 4-methylthiophenyl carbamate (Mtpc), 2,4-dimethylthiophenyl carbamate (Bmpc), 2-phosphonioethyl carbamate (Peoc), 2-triphenylphosphonioisopropyl carbamate (Ppoc), l,l-dimethyl-2-cyanoethyl carbamate, m-chloro-p-acyloxybenzyl carbamate, p-(dihydroxyboryl)benzyl carbamate, 5-benzisoxazolylmethyl carbamate, 2-(trifluoromethyl)-6-chromonylmethyl carbamate (Tcroc), m-nitrophenyl carbamate, 3,5-dimethoxybenzyl carbamate, o-nitrobenzyl carbamate, 3,4-dimethoxy-6-nitrobenzyl carbamate, phenyl(o-nitrophenyl)methyl carbamate, phenothiazinyl-(10)-carbonyl derivative, N'-p-toluenesulfonylaminocarbonyl derivative, N'-phenylaminothiocarbonyl derivative, t-amyl carbamate, S-benzyl thiocarbamate, p-cyanobenzyl carbamate, cyclobutyl carbamate, cyclohexyl carbamate, cyclopentyl carbamate, cyclopropylmethyl carbamate, p-decyloxybenzyl carbamate, 2,2-dimethoxycarbonylvinyl carbamate, o-(N,N-dimethylcarboxamido)benzyl carbamate, l,l-dimethyl-3- (N,N-dimethylcarboxamido)propyl carbamate, 1,1-dimethylpropynyl carbamate, di(2-pyridyl)methyl carbamate, 2-furanylmethyl carbamate, 2-iodoethyl carbamate, isoborynl carbamate, isobutyl carbamate, isonicotinyl carbamate, p-(p '-methoxyphenylazo)benzyl carbamate, 1-methylcyclobutyl carbamate, 1-methylcyclohexyl carbamate, 1 -methyl- 1 -cyclopropylmethyl carbamate, l-methyl-1-(3,5-dimethoxyphenyl)ethyl carbamate, 1 -methyl- l-(p-phenylazophenyl)ethyl carbamate, 1 -methyl- 1-phenylethyl carbamate, 1 -methyl- l-(4-pyridyl)ethyl carbamate, phenyl carbamate, p-(phenylazo)benzyl carbamate, 2,4,6-tri-t-butylphenyl carbamate, 4- (trimethylammonium)benzyl carbamate, 2,4,6-trimethylbenzyl carbamate, formamide, acetamide, chloroacetamide, trichloroacetamide, trifluoroacetamide, phenylacetamide, 3- phenylpropanamide, picolinamide, 3-pyridylcarboxamide, N-benzoylphenylalanyl derivative, benzamide, p-phenylbenzamide, o-nitophenylacetamide, o-nitrophenoxyacetamide, acetoacetamide,
(N'-dithiobenzyloxycarbonylamino)acetamide, 3-(p-hydroxyphenyl)propanamide, 3- (o-nitrophenyl)propanamide, 2-methyl-2-(o-nitrophenoxy)propanamide, 2-methyl-2-(o-phenylazophenoxy)propanamide, 4-chlorobutanamide, 3 -methyl-3 - nitrobutanamide, o-nitrocinnamide, N-acetylmethionine derivative, o-nitrobenzamide, o-(benzoyloxymethyl)benzamide, 4,5-diphenyl-3-oxazolin-2-one, N-phthalimide,
N-dithiasuccinimide (Dts), N-2,3-diphenylmaleimide, N-2,5-dimethylpyrrole, N-1, 1,4,4- tetramethyldisilylazacyclopentane adduct (STABASE), 5-substituted 1,3-dimethyl-1,3,5- triazacyclohexan-2-one, 5-substituted 1,3-dibenzyl-1,3,5-triazacyclohexan-2-one, 1- substituted 3,5-dinitro-4-pyridone, N-methylamine, N-allylamine, N-[2-(trimethylsilyl)ethoxy]methylamine (SEM), N-3-acetoxypropylamine,
N-(l-isopropyl-4-nitro-2-oxo-3-pyroolin-3-yl)amine, quaternary ammonium salts, N-benzylamine, N-di(4-methoxyphenyl)methylamine, N-5-dibenzosuberylamine, N-triphenylmethylamine (Tr), N-[(4-methoxyphenyl)diphenylmethyl]amine (MMTr), N-9-phenylfluorenylamine (PhF), N-2,7-dichloro-9-fluorenylmethyleneamine, N-ferrocenylmethylamino (Fcm), N-2-picolylamino N'-oxide, N- 1 , 1 -dimethylthiomethyleneamine, N-benzylideneamine, N-p-methoxybenzylideneamine, N-diphenylmethyleneamine, N-[(2-pyridyl)mesityl]methyleneamine, N-(N',N'-dimethylaminomethylene)amine, NN'-isopropylidenediamine, N-p-nitrobenzylideneamine, N-salicylideneamine, N-5- chlorosalicylideneamine, N-(5 -chloro-2-hydroxyphenyl)phenylmethyleneamine,
N-cyclohexylideneamine, N-(5 ,5 -dimethyl-3 -oxo- 1 -cyclohexenyl)amine, N-borane derivative, N-diphenylborinic acid derivative, N-[phenyl(pentacarbonylchromium- or tungsten)carbonyl]amine, N-copper chelate, N-zinc chelate, N-nitroamine, N-nitrosoamine, amine N-oxide, diphenylphosphinamide (Dpp), dimethylthiophosphinamide (Mpt), diphenylthiophosphinamide (Ppt), dialkyl phosphoramidates, dibenzyl phosphoramidate, diphenyl phosphoramidate, benzenesulfenamide, o-nitrobenzenesulfenamide (Νps), 2,4-dinitrobenzenesulfenamide, pentachlorobenzenesulfenamide, 2-nitro-4-methoxybenzenesulfenamide, triphenylmethylsulfenamide, 3-nitropyridinesulfenamide (Npys), p-toluenesulfonamide (Ts), benzenesulfonamide, 2,3,6,-trimethyl-4-methoxybenzenesulfonamide (Mtr), 2,4,6- trimethoxybenzenesulfonamide (Mtb), 2,6-dimethyl-4-methoxybenzenesulfonamide (Pme), 2,3,5,6-tetramethyl-4-methoxybenzenesulfonamide (Mte), 4- methoxybenzenesulfonamide (Mbs), 2,4,6-trimethylbenzenesulfonamide (Mts), 2,6- dimethoxy-4-methylbenzenesulfonamide (iMds), 2,2,5,7,8-pentamethylchroman-6- sulfonamide (Pmc), methanesulfonamide (Ms), β-trimethylsilylethanesulfonamide (SES), 9-anthracenesulfonamide, 4-(4',8'-dimethoxynaphthylmethyl)benzenesulfonamide (DNMBS), benzylsulfonamide, trifluoromethylsulfonamide, and phenacylsulfonamide. Exemplary protecting groups are detailed herein, however, it will be appreciated that the present invention is not intended to be limited to these protecting groups; rather, a variety of additional equivalent protecting groups can be readily identified using the above criteria and utilized in the method of the present invention. Additionally, a variety of protecting groups are described in Protecting Groups in Organic Synthesis, T. W. Greene and P. G. M. Wuts, 3rd edition, John Wiley & Sons, 1999, the entirety of which is incorporated herein by reference.
When substituents are described herein, the term "radical" or "optionally substituted radical" is sometimes used. In this context, "radical" means a moiety or functional group having an available position for attachment to the structure on which the substituent is bound. In general the point of attachment would bear a hydrogen atom if the substituent were an independent neutral molecule rather than a substituent. The terms "radical" or "optionally-substituted radical" in this context are thus interchangeable with "group" or "optionally-substituted group".
As described herein, compounds of the invention may contain "optionally substituted" moieties. In general, the term "substituted", whether preceded by the term "optionally" or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted group'Or "optionally substituted radical" may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds. The term "stable", as used herein, refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.
In some chemical structures herein, substituents are shown attached to a bond that crosses a bond in a ring of the depicted molecule. This convention indicates that one or more of the substituents may be attached to the ring at any available position (usually in place of a hydrogen atom of the parent structure). In cases where an atom of a ring so substituted has two substitutable positions, two groups may be present on the same ring atom. Unless otherwise indicated, when more than one substituent is present, each is defined independently of the others, and each may have a different structure. In cases where the substituent shown crossing a bond of the ring is -R, this has the same meaning as if the ring were said to be "optionally substituted" as described in the preceding paragraph.
Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are independently halogen; -(CH2)0-4R°; -(CH2V4ORo;
-0-(CH2)o-4C(0)ORo; -(CH2)o-4CH(ORo)2; -(CH2)0-4SRo; -(CH2V4Ph, which may be substituted with R°; -(CH2V4O(CH2ViPh which may be substituted with R°;
-CH=CHPh, which may be substituted with R°; -NO2; -CN; -N3; -(CH2)o.4N(Ro)2;
-(CH2)o-4N(Ro)C(0)Ro; -N(R°)C(S)R°; -(CH2)o-4N(Ro)C(0)NRo 2; -N(R°)C(S)NR°2;
-(CH2)o-4N(Ro)C(0)ORo; -N(R°)N(R°)C(0)R°; -N(Ro)N(R°)C(0)NRo 2;
-N(R°)N(R°)C(0)0R°; -(CH2V4C(O)Ro; -C(S)Ro; -(CH2V4C(O)ORo; -(CH2)o-4C(0)N(R°)2; -(CH2V4C(O)SRo; -(CH2)o.4C(0)OSiRo 3; -(CH2V4OC(O)Ro;
-OC(O)(CH2V4SR-, SC(S)SRo; -(CH2)O-4SC(O)Ro; -(CH2)0-4C(O)NR°2; -C(S)NR°2;
-C(S)SRo; -SC(S)SRo, -(CH2)o-4OC(0)NRo 2; -C(0)N(0R°)R°; -C(O)C(O)Ro;
-C(O)CH2C(O)Ro; -C(N0R°)R°; -(CH2V4SSRo; -(CH2V4S(O)2Ro; -(CH2V4S(O)2ORo;
-(CH2)O-4OS(O)2Ro; -S(O)2NR°2; -(CH2V4S(O)Ro; -N(R°)S(O)2NR°2; -N(R°)S(0)2R°; -N(0R°)R°; -C(NH)NR°2; -P(O)2Ro; -P(O)R°2; -OP(O)R°2; -OP(O)(OR°)2; SiR°3; -(C1-4 straight or branched alkylene)O-N(R°)2; or -(C1-4 straight or branched alkylene)C(O)O-N(R°)2, wherein each Ro may be substituted as defined below and is independently hydrogen, C1-4 aliphatic, -CH2Ph, -0(CH2)o-iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrences of Ro, taken together with intervening atom(s), form a 3-12- membered saturated, partially unsaturated, or aryl mono- or polycyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, which may be substituted as defined below.
Suitable monovalent substituents on Ro (or the ring formed by taking two independent occurrences of Ro together with their intervening atoms), are independently halogen, -(CH2)0_2R●, -(haloR●), -(CH2)0_2OH, -(CH2)0_2OR●, -(CH2)0_2CH(OR●)2; -O(haloR'), -CN, -N3, -(CH2)0.2C(O)R●, -(CH2)0.2C(O)OH, -(CH2)0.2C(O)OR●, -(CH2)o-4C(0)N(R°)2; -(CH2)0.2SR●, -(CH2)0.2SH, -(CH2)0.2NH2, -(CH2V2NHR●, -(CH2)o-2NR●2, -NO2, -SiR● 3, -OSiR● 3, -C(O)SR●, -( C1-4 straight or branched alkylene)C(O)OR●, or -SSR● wherein each R● is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently selected from C1-4 aliphatic, -CH2Ph, -0(CH2)o-iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. Suitable divalent substituents on a saturated carbon atom of Ro include =0 and =S.
Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include the following: =0, =S, =NNR* 2, =NNHC(O)R*, =NNHC(O)OR*, =NNHS(O)2R*, =NR*, =NOR*, -O(C(R* 2))2-3O-, or -S(C(R* 2))2-3S-, wherein each independent occurrence of R is selected from hydrogen, C1-6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. Suitable divalent substituents that are bound to vicinal substitutable carbons of an "optionally substituted" group include: -O(CR* 2)2-3O-, wherein each independent occurrence of R is selected from hydrogen, C1-6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
Suitable substituents on the aliphatic group of R* include halogen, -R●, -(haloR●), -OH, -OR●, -O(haloR'), -CN, -C(O)OH, -C(O)OR●, -NH2, -NHR●, -NR● 2, or -NO2, wherein each R● is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently C1-4 aliphatic, -CH2Ph, -0(CH2)0-1Ph, or a 5- 6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include -Rf, -NRf 2, -C(O)Rf, -C(O)ORf, -C(O)C(O)Rf, -C(O)CH2C(O)Rf, -S(O)2Rf; -S(O)2NRf 2, -C(S)NRf 2, -C(NH)NRf 2, or -N(Rf)S(O)2Rf; wherein each Rf is independently hydrogen, C1-6 aliphatic which may be substituted as defined below, unsubstituted -OPh, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrences of Rf, taken together with intervening atom(s) form an unsubstituted 3-12-membered saturated, partially unsaturated, or aryl mono- or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. A substitutable nitrogen may be substituted with three Rf substituents to provide a charged ammonium moiety -N+(Rf)3, wherein the ammonium moiety is further complexed with a suitable counterion.
Suitable substituents on the aliphatic group of Rf are independently halogen, -R●, -(haloR●), -OH, -OR●, -O(haloR'), -CN, -C(O)OH, -C(O)OR●, -NH2, -NHR●, -NR● 2, or -NO2, wherein each R● is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently C1-4 aliphatic, -CH2Ph, -O(CH2)0_iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
As used herein, the term "catalyst" refers to a substance the presence of which increases the rate and/or extent of a chemical reaction, while not being consumed or undergoing a permanent chemical change itself. As used herein, the term "multidentate" refers to ligands having multiple sites capable of coordinating to a single metal center.
As used herein, the term "activating moiety" refers to a moiety comprising one or more activating functional groups. In certain embodiments, an activating moiety improves the catalytic activity of a metal complex. In some embodiments, such improved catalytic activity is characterized by higher conversion of starting materials compared to a metal complex lacking an activating moiety. In some embodiments, such improved catalytic activity is characterized by higher rate of conversion of starting materials compared to a metal complex lacking an activating moiety. In some embodiments, such improved catalytic activity is characterized by higher yield of product compared to a metal complex lacking an activating moiety.
Detailed Description of Certain Embodiments
The present invention provides, among other things, unimolecular metal complexes for the copolymerization of carbon dioxide and epoxides and methods of using the same. In certain embodiments, provided metal complexes contain a metal- ligand moiety tethered to one or more activating moieties. In some embodiments, an activating moiety comprises a linker and one or more activating functional groups. In some embodiments, provided metal complexes act as polymerization catalysts. In certain embodiments, at least one activating functional group present on the tethered moiety can act as a polymerization co-catalyst and thereby increase the rate of the copolymerization.
In certain embodiments, provided metal complexes include a metal atom coordinated to a multidentate ligand and at least one activating moiety tethered to the multidentate ligand. In certain embodiments, provided metal complexes have the structure:
Figure imgf000027_0001
wherein:
M is a metal atom;
comprises a multidentate ligand; (Z)m represents one or more activating moieties attached to the multidentate ligand, where
Figure imgf000028_0001
is a linker moiety covalently coupled to the ligand, each Z is an activating functional group; and m is an integer from 1 to 4 representing the number of Z groups present on an individual linker moiety.
In certain embodiments, provided metal complexes include a metal atom coordinated to a multidentate ligand and at least one activating moiety tethered to the multidentate ligand. In some embodiments, there are 1 to 10 activating moieties (Z)m tethered to the multidentate ligand. In certain embodiments, there are 1 to 8 such activating moieties tethered to the multidentate ligand. In certain embodiments, there are 1 to 4 such activating moieties tethered to the multidentate ligand.
/. Activating Functional Groups
In some embodiments, an activating functional group is selected from the group consisting of neutral nitrogen-containing functional groups, cationic moieties, phosphorous-containing functional groups, and combinations of two or more of these.
La. Neutral Nitrogen-Containing Activating Groups
In some embodiments, one or more tethered activating functional groups on provided metal complexes are neutral nitrogen-containing moieties. In some embodiments, such moieties include one or more of the structures in Table Z-I :
Figure imgf000029_0001
or a combination of two or more of these,
TABLE Z-I
wherein:
each occurrence of R1, and R2 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein two or more R1 and R2 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms;
each occurrence of R5 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-
14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly eye lie saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein an R5 group can be taken with an R1 or R2 group to form one or more optionally substituted rings;
each occurrence of R7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C1--20 acyl; C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
In some embodiments, an activating functional group is an N-linked amino
group ,
Figure imgf000030_0001
where R1 and R2 are as defined above.
In certain embodiments, R1 and R2 are both hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl.
In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and
-CH2NRyCH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
In specific embodiments, an N-linked amine activating functional group is selected from the group consisting of:
Figure imgf000033_0001
In some embodiments, one or more activating functional groups is an //-linked
hydroxy 1 amine derivative:
Figure imgf000033_0002
;
wherein R1 and R7 are as defined above.
In certain embodiments, R7 is hydrogen. In some embodiments, R7 is an optionally substituted radical selected from the group consisting of C1-12 aliphatic, phenyl, 8- to 10-membered aryl, and 3- to 7-memered heterocyclic. In certain embodiments, R7 is a C1-12 aliphatic. In certain embodiments, R7 is a C1-6 aliphatic. In some embodiments, R7 is an optionally substituted 8- to 10-membered aryl group. In certain embodiments, R7 is an optionally substituted phenyl. In some embodiments, R7 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl.
In certain embodiments, R1 is hydrogen. In some embodiments, R1 is an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to
7-membered heterocyclic. In some embodiments, R1 is an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In some embodiments, R1 is an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, R1 is an optionally substituted C1--20 aliphatic. In certain embodiments, R1 is an optionally substituted C1-12 aliphatic. In some embodiments, R1 is an optionally substituted C1-6 aliphatic. In some embodiments, R1 is an optionally substituted C1-12 heteroaliphatic. In some embodiments, R1 is an optionally substituted 8- to 10-membered aryl. In certain embodiments, R1 is an optionally substituted phenyl. In some embodiments, R1 is an optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R1 is an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 is butyl. In some embodiments, R1 is isopropyl. In some embodiments, R1 is phenyl. In some embodiments, R1 is benzyl.In some embodiments, R1 is perfluoro. In some embodiments, R1 is -CF2CFs. In certain embodiments, R1 and R7 are taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms.
In certain embodiments, one or more N-linked hydroxyl amine activating functional groups are selected from the group consisting of:
Figure imgf000035_0001
In some embodiments, an activating functional group in a provided metal complexis an amidine. In certain embodiments, such amidine activating functional groups
are selected from:
Figure imgf000035_0002
where each occurrence of R1, R2 and R5 are as defined above.
In certain embodiments, each R1 and R2 is hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, each R1 and R2 is independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In some embodiments, each R1 and R2 is independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to
12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl. In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and -CH2NRyCH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
In certain embodiments, R5 is H. In certain embodiments, R5 is optionally substituted C1--20 aliphatic. In some embodiments, R5 is optionally substituted 6- to 14- membered aryl. In certain embodiments, R5 is optionally substituted C1-12 aliphatic. In some embodiments, R5 is optionally substituted C1-6 aliphatic. In certain embodiments, R5 is optionally substituted phenyl.
In some embodiments, one or more R1 or R2 groups are taken together with R5 and intervening atoms to form an optionally substituted ring. In certain embodiments, R1 and R5 are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, R2 and R5 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms. In some embodiments, R1, R2 and R5 are taken together to form an optionally substituted fused ring system. In some embodiments such rings formed by combinations of any of R1, R2 and R5 are partially unsaturated or aromatic.
In certain embodiments, an activating functional group is an //-linked amidine:
Figure imgf000037_0001
. In certain embodiments, //-linked amidine groups are selected from the group consisting of:
Figure imgf000038_0001
In certain embodiments, activating functional groups are amidine moieties linked
N through the imine nitrogen: N R5.
In certain embodiments, imine-linked amidine activating functional groups are selected from the group consisting of:
Figure imgf000039_0001
In certain embodiments, activating functional groups are amidine moieties linked
through a carbon atom:
Figure imgf000039_0003
. In certain embodiments, carbon-linked amidine activating groups are selected from the group consisting of:
Figure imgf000039_0002
In some embodiments, one or more activating functional groups is a carbamate. In
certain embodiments, a carbamate is N-linked where R1 and R2 are as
Figure imgf000040_0001
defined above. In some embodiments, a carbamate is O-linked:
Figure imgf000040_0002
, where R and R2 are as defined above.
In certain embodiments, R1 and R2 are both hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In some embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to
12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl.
In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and
-CH2NRyCH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle. In some embodiments, R2 is selected from the group consisting of: methyl, t-butyl, t-amyl, benzyl, adamantyl, allyl, 4-methoxycarbonylphenyl, 2-(methylsulfonyl)ethyl, 2-(4-biphenylyl)-prop-2-yl, 2-(trimethylsilyl)ethyl, 2-bromoethyl, and 9-fluorenylmethyl. In some embodiments, an activating functional group is a guanidine or bis- guanidine group:
Figure imgf000042_0001
where each occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more
R1, R1 , R2, R2 , R2 -, R3, and R3 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms;
In certain embodiments, each occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is hydrogen. In some embodiments, each occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; 3- to 7-membered heterocyclic, phenyl, and 8- to 10- membered aryl. In some embodiments, each occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is hydrogen or an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In certain embodiments, each occurrence of R1, R1 , R2,
R2 , R2 , R3, and R3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic, phenyl, and 8- to 10-membered aryl. In certain embodiments, each occurrence of R1 and R2 is independently an optionally hydrogen or an optionally substituted C1-8 aliphatic, phenyl, or 8- to 10-membered aryl group. In some embodiments, each occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is independently hydrogen or an optionally substituted C1--20 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently hydrogen an optionally substituted aryl group or an optionally substituted C1-8 aliphatic group. In some embodiments, each occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is independently hydrogen or an optionally substituted C1-6 aliphatic group. In some embodiments, each occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is independently hydrogen or an optionally substituted C1-4 aliphatic group. In some embodiments, each occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1, R1 , R2, R2 , R2 , R3, and R3 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1, R1', R2, R2', R2 -, R3, and R3' are each independently optionally substituted C1-6 aliphatic. In some embodiments, one or more occurrence of R1 , R2, R2 , R2 , R3, and R3 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, one or more occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is independently hydrogen or an optionally substituted phenyl or 8- to 10- membered aryl. In some embodiments, one or more occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is independently hydrogen, or an optionally substituted 5- to 10-membered heteroaryl.
In some embodiments, R1 is optionally substituted C1-6 aliphatic. In certain embodiments, R1 is optionally substituted C1-6 aliphatic. In certain embodiments, R2 is optionally substituted C1-6 aliphatic. In certain embodiments, R2 is optionally substituted C1-6 aliphatic. In certain embodiments, R2 is optionally substituted C1-6 aliphatic. In certain embodiments, R is optionally substituted C1-6 aliphatic. In certain embodiments, R3 is optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1, R1 , R2, R2 , R2 , R3, and R3 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In certain embodiments, R1, R1 , R2, R2 , R2 , R3, and R3 are each methyl or ethyl. In some embodiments, one or more R1, R1 , R2, R2', R2-, R3, and R3' is perfluoro.
In some embodiments, any two or more R1, R1 , R2, R2 , R2 , R3, and R3 groups are taken together with intervening atoms to form one or more optionally substituted rings.
In certain embodiments, R1 and R2 are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In some embodiments, R2 and R2 are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In certain embodiments, R1 and R3 are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In some embodiments, [R2 and R2 ] and [R1 and R3] are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In some embodiments, three or more R1, R1 , R2, R2 , R2 , R3, and R3 groups are taken together with any intervening atoms to form optionally substituted rings. In certain embodiments, R1 and R2 groups are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, three or more R1 and/or R2 groups are taken together to form an optionally substituted fused ring system.
In certain embodiments where an activating functional group is a guanidine or bis guanidine moiety, it is chosen from the group consisting of:
Figure imgf000045_0001
In some embodiments, an activating functional group is a urea:
Figure imgf000045_0002
where R1, and R2 are as defined above.
In certain embodiments, R1 and R2 are each hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl. In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and -CH2NRyCH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
In certain embodiments, activating functional groups are oxime or hydrazone
Figure imgf000047_0001
or groups:
Figure imgf000047_0002
where R1, R2, R5, and R7 are as defined above.
In certain embodiments, R1 and R2 are both hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, 5- to 14-membered heteroaryl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl.
In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and -CH2NR7CH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
In certain embodiments, R5 is H. In certain embodiments, R5 is optionally substituted C1--20 aliphatic, and in some embodiments R5 is optionally substituted 6- to 14- membered aryl. In certain embodiments, R5 is optionally substituted C1-12 aliphatic and in some embodiments, optionally substituted C1-6 aliphatic. In certain embodiments, R5 is optionally substituted phenyl.
In some embodiments, one or more R1 or R2 groups are taken together with R5 and intervening atoms to form an optionally substituted ring. In certain embodiments, R1 and R5 are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, R2 and R5 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms. In some embodiments, R1, R2 and R5 are taken together to form an optionally substituted fused ring system. In some embodiments such rings formed by combinations of any of R1, R2 and R5 are partially unsaturated or aromatic.
In certain embodiments, R7 is -H. In certain embodiments, R7 is optionally substituted C1--20 aliphatic, while in some embodiments R5 is optionally substituted 6- to 14-membered aryl. In certain embodiments, R7 is optionally substituted C1-12 aliphatic or in some embodiments, optionally substituted C1-6 aliphatic. In certain embodiments, R7 is optionally substituted C1-12 acyl or in some embodiments, optionally substituted C1-6 acyl. In certain embodiments, R7 is optionally substituted phenyl. In some embodiments, R7 is a hydroxyl protecting group. In some embodiments, R7 is a silyl protecting group.
In some embodiments, an activating functional group is an N-oxide derivative:
Figure imgf000049_0001
, where R1 and R2 are as defined above. In certain embodiments, R1 and R2 are both hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, or 8- to 10- membered aryl and 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl.
In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and -CH2NRyCH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
In specific embodiments, an JV-oxide activating functional group is selected from the group consisting of:
Figure imgf000052_0001
Lb. Cationic Activating Groups
In some embodiments, one or more tethered activating functional groups on provided metal complexes are cationic moieties include cationic moieties. In some embodiments, such moieties include one or more of the structures in Table Z-2:
Figure imgf000054_0001
Figure imgf000054_0002
and
Figure imgf000054_0003
or a combination of two or more of these,
Figure imgf000054_0004
TABLE Z-2 wherein: each occurrence of R1, R2, and R3 is as previously defined; R4 is hydrogen, hydroxyl, optionally substituted C1--20 aliphatic;
each occurrence of R5 and R6 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein R5 and R6 can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, and an R5 or R6 group can be taken with an R1 or R2 group to form one or more optionally substituted rings;
each occurrence of R8, R9, and R10 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12- membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more R8, R9 and R10 groups can be taken together with intervening atoms to form one or more optionally substituted rings; each occurance of R11 is independently selected from the group consisting of: halogen, -NO2, -CN, -SRy, -S(O)Ry, -S(O)2Ry, -NRyC(0)Ry, -OC(O)Ry, -CO2Ry, -NCO, -N3, -OR7, -0C(0)N(Ry)2, -N(Ry)2, -NRyC(O)Ry, -NRyC(0)0Ry; or an optionally substituted radical selected from the group consisting of C1-20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a
6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where each occurrence of Ry is independently hydrogen or an optionally substituted C1-6 aliphatic group, and where two or more adjacent R11 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12- membered ring containing 0 to 4 heteroatoms;
X- is any anion, and
Ring A is an optionally substituted, 5- to 10-membered heteroaryl group.
In certain embodiments, a cationic activating functional group is a protonated
i 2 amine:
Figure imgf000056_0001
where R and R are as defined above.
In certain embodiments, R1 and R2 are both hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, or 8- to 10- membered aryl and 3- to 7-membered heterocyclic. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl.
In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and -CH2NRyCH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
In specific embodiments, a protonated amine activating functional group is selected from the group consisting of:
Figure imgf000059_0001
In certain embodiments, an activating functional group is a guanidinium
Figure imgf000059_0002
group: . In some embodiments, each of R4, R5, R6, R7, and R8 is hydrogen.
In some embodiments, each occurrence of R4, R5, R6, R7, and R8 is independently hydrogen or C1--20 aliphatic. In some embodiments, each occurrence of R4, R5, R6, R7, and R8 is independently hydrogen or C1-12 aliphatic. In some embodiments, each occurrence of R4, R5, R6, R7, and R8 is independently hydrogen or C1--20 heteroaliphatic. In some embodiments, each occurrence of R4, R5, R6, R7, and R8 is independently hydrogen or phenyl. In some embodiments, each occurrence of R4, R5, R6, R7, and R8 is independently hydrogen or 8- to 10-membered aryl. In some embodiments, each occurrence of R4, R5, R6, R7, and R8 is independently hydrogen or 5- to 10-membered heteroaryl. In some embodiments, each occurrence of R4, R5, R6, R7, and R8 is independently hydrogen or 3- to 7-membered heterocyclic. In some embodiments, one or more of R4, R5, R6, and R7 is optionally substituted C1-12 aliphatic. In certain embodiments, any of (R4 and R5), (R5 and R6), (R6 and R7), (R7 and R8), and (R4 and R7) can be taken together with intervening atoms to form one or more optionally substituted rings. In some embodiments, (R4 and R5) and (R6 and R7) are taken together to form rings.
It will be appreciated that when a guanidinium cation is depicted as
Figure imgf000060_0003
, all such resonance forms are contemplated and encompassed by the
present disclosure. For example, such groups can also be depicted as
Figure imgf000060_0001
Figure imgf000060_0002
In specific embodiments, a guanidinium activating functional group is selected from the group consisting of:
Figure imgf000061_0003
Figure imgf000061_0001
In some embodiments, an activating functional group is a sulfonium group or an
arsonium group:
Figure imgf000061_0002
, where R8, R9, and R10 are as defined above.
In certain embodiments, each occurrence of R8, R9, and R10 is independently optionally substituted C1--20 aliphatic. In some embodiments, each occurrence of R8, R9, and R10 is independently hydrogen or optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R9, R10, and R11 is independently hydrogen or optionally substituted phenyl. In some embodiments, each occurrence of R9, R10, and R11 is independently hydrogen or optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R8, R9, and R10 is independently hydrogen or optionally substituted 5- to 10-membered heteroaryl. In some embodiments, each occurrence of R9, R10, and R11 is independently hydrogen or optionally substituted 3- to 7-membered heterocyclic. In some embodiments, R8 and R9 are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3_Ci4 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted C6-CiO aryl, and optionally substituted 5- to 10-membered heteroaryl. In certain embodiments, R8, R9 and R10 are each methyl. In certain embodiments, R8, R9 and R10 are each phenyl.
In specific embodiments, an arsonium activating functional group is selected from the group consisting of:
Figure imgf000062_0001
In some embodiments, an activating functional group is an optionally substituted nitrogen-containing heterocycle. In certain embodiments, the nitrogen-containing heterocycle is an aromatic heterocycle. In certain embodiments, the optionally substituted nitrogen-containing heterocycle is selected from the group consisting of: pyridine, imidazole, pyrrolidine, pyrazole, quinoline, thiazole, dithiazole, oxazole, triazole, pyrazolem, isoxazole, isothiazole, tetrazole, pyrazine, thiazine, and triazine.
In some embodiments, a nitrogen-containing heterocycle includes a quaternarized nitrogen atom. In certain embodiments, a nitrogen-containing heterocycle includes an
iminium moiety such as
Figure imgf000062_0002
. In certain embodiments, the optionally substituted nitrogen-containing heterocycle is selected from the group consisting of pyridinium, imidazolium, pyrrolidinium, pyrazolium, quinolinium, thiazolium, dithiazolium, oxazolium, triazolium, isoxazolium, isothiazolium, tetrazolium, pyrazinium, thiazinium, and triazinium.
In certain embodiments, a nitrogen-containing heterocycle is linked to a metal complex via a ring nitrogen atom. In some embodiments, a ring nitrogen to which the attachment is made is thereby quaternized, and in some embodiments, linkage to a metal complex takes the place of an N-H bond and the nitrogen atom thereby remains neutral. In certain embodiments, an optionally substituted //-linked nitrogen-containing heterocycle is a pyridinium derivative. In certain embodiments, optionally substituted N- linked nitrogen-containing heterocycle is an imidazolium derivative. In certain embodiments, optionally substituted N-linked nitrogen-containing heterocycle is a thiazolium derivative. In certain embodiments, optionally substituted N-linked nitrogen- containing heterocycle is a pyridinium derivative.
In some embodiments, an activating functional group is
Figure imgf000063_0003
. In certain embodiments, ring A is an optionally substituted, 5- to 10-membered heteroaryl group. In some embodiments, Ring A is an optionally substituted, 6-membered heteroaryl group. In some embodiments, Ring A is a ring of a fused heterocycle. In some embodiments, Ring A is an optionally substituted pyridyl group.
In some embodiments, R12 is hydrogen. In some embodiments, R12 is an optionally substituted C1--20 aliphatic group. In some embodiments, R12 is C1--20 heteroaliphatic. In some embodiments, R12 is optionally substituted phenyl, 8- to 10- membered aryl; 5- to 10-membered heteroaryl. In some embodiments, R12 is 3- to 7- membered heterocyclic. In some embodiments, R12 is an optionally substituted C1-12 aliphatic group. In some embodiments, R12 is neopentyl. In some embodiments, R12 is oxide or hydroxyl.
In some embodiments, when Z is
Figure imgf000063_0001
i , ring A is other than an imidazole, an oxazole, or a thiazole.
In specific embodiments, a nitrogen-containing heterocycle activating functional group is selected from the group consisting of:
Figure imgf000063_0002
Figure imgf000064_0001
In some embodiments, an activating functional group is
Figure imgf000064_0002
or where R1, R2 and R5 are as defined above.
In certain embodiments, R1 and R2 are each hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl.
In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and -CH2NRyCH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
In certain embodiments, R5 is H. In certain embodiments, R5 is optionally substituted C1--20 aliphatic, and in some embodiments R5 is optionally substituted 6- to 14- membered aryl. In certain embodiments, R5 is optionally substituted C1-12 aliphatic and in some embodiments, optionally substituted C1-6 aliphatic. In certain embodiments, R5 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R5 is perfluoro. In some embodiments, R5 is-CF2CF3.In certain embodiments, R5 is optionally substituted phenyl.
In some embodiments, one or more R1 or R2 groups are taken together with R5 and intervening atoms to form an optionally substituted ring. In certain embodiments, R1 and R5 are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, R2 and R5 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms. In some embodiments, R1, R2 and R5 are taken together to form an optionally substituted fused ring system. In some embodiments such rings formed by combinations of any of R1, R2 and R5 are partially unsaturated or aromatic.
In some embodiments, an activating functional group is
Figure imgf000066_0001
, where R1 and
R2 are as defined above.
In certain embodiments, R1 and R2 are each independently an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic; phenyl; and 8-10-membered aryl. In some embodiments, R1 and R2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R1 and R2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-C14 carbocycle, optionally substituted C3-C14 heterocycle, optionally substituted C6-CiO aryl, and optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R1 and R2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R1 and R2 is independently perfluoro. In some embodiments, each occurrence of R1 and R2 is independently -CF2CF3.
In some embodiments, an activating functional group is
Figure imgf000067_0001
where R , R , R3, and R5 are as defined above.
In certain embodiments, R1, R2, and R3 are each independently an optionally substituted group selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; and 8- 10-membered aryl. In certain embodiments, R1, R2, and R3 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R1 and R2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-Ci4 carbocycle, optionally substituted C3-Ci4 heterocycle, optionally substituted C6-CiO aryl, and optionally substituted 5- to 10-membered heteroaryl. In certain embodiments, R1, R2, and R are each independently an optionally substituted C1-6 aliphatic. In certain embodiments, R1, R2, and R3 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In certain embodiments, R1, R2, and R3 are each independently perfluoro. In some embodiments, R1, R2, and R3 are each independently -CF2CF3.
In certain embodiments, R5 is hydrogen. In certain embodiments R5 is an optionally substituted group selected from the group consisting of C1-i2 aliphatic and C1-i2 heteroaliphatic. In some embodiments, R5 is an optionally substituted Cn2 aliphatic. In some embodiments, R5 is optionally substituted C1-6 aliphatic. In some embodiments, an activating functional group is
Figure imgf000068_0001
. In certain embodiments, R1 and R2 are each independently an optionally substituted group selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; and 8-10- membered aryl. In some embodiments, R1 and R2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R1 and R2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-Ci4 carbocycle, optionally substituted C3-Ci4 heterocycle, optionally substituted C6-CiO aryl, and optionally substituted 5- to 10- membered heteroaryl. In some embodiments, R1 and R2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R1 and R2 is independently perfluoro. In some embodiments, each occurrence of R1 and R2 is independently -CF2CF3.
In certain embodiments, R5 and R6 are each independently an optionally substituted group selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl, and 8-10-membered aryl. In some embodiments, R5 and R6 are each independently an optionally substituted C1--20 aliphatic. In some embodiments, R5 and R6 are each independently an optionally substituted C1--20 heteroaliphatic having. In some embodiments, R5 and R6 are each independently an optionally substituted phenyl or 8-10-membered aryl. In some embodiments, R5 and R6 are each independently an optionally substituted 5- tolO-membered heteroaryl. In some embodiments, R3 and R4 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-Ci4 carbocycle, optionally substituted C3- Ci4 heterocycle, optionally substituted C6-CiO aryl, and optionally substituted 5- to 10- membered heteroaryl. In some embodiments, R5 and R6 are each independently an optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R5 and R6 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R5 and R6 is independently perfluoro. In some embodiments, each occurrence of R5 and R6 is independently -CF2CF3. In some embodiments, an activating functional group is
Figure imgf000069_0001
where R1 and R2 are as defined above.
In certain embodiments, R1 and R2 are each hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl or 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic. In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl.
In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and -CH2NRyCH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.
In some embodiments, an activating functional group is
Figure imgf000070_0001
In certain embodiments, R1, R2, and R3 are each independently an optionally substituted group selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; and 8- 10-membered aryl. In certain embodiments, R1, R2, and R3 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R1 and R2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-C14 carbocycle, optionally substituted C3- C14 heterocycle, optionally substituted C6-CiO aryl, and optionally substituted 5- to 10- membered heteroaryl. In certain embodiments, R1, R2, and R3 are each independently an optionally substituted C1-6 aliphatic. In certain embodiments, R1, R2, and R3 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In certain embodiments, R1, R2, and R3 are each independently perfluoro. In some embodiments, R1, R2, and R3 are each independently - CF2CF3.
In some embodiments, an activating functional group is
Figure imgf000071_0001
Figure imgf000071_0002
, where R1 and R2 are as defined above.
In certain embodiments, R1 and R2 are each hydrogen. In some embodiments, only one of R1 and R2 is hydrogen. In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic, phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
In certain embodiments, R1 and R2 are each independently an optionally substituted radical selected from the group consisting of C1-12 aliphatic and C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-12 aliphatic. In some embodiments, R1 and R2 are each independently optionally substituted C1-6 aliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1--20 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted C1-12 heteroaliphatic. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R1 and R2 is independently an optionally substituted 3- to 7-membered heterocyclic.
In certain embodiments, R1 and R2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R1 and R2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R1 and R2 are each butyl. In some embodiments, R1 and R2 are each isopropyl. In some embodiments, R1 and R2 are perfluoro. In some embodiments, R1 and R2 are -CF2CF3. In some embodiments, R1 and R2 are each phenyl. In some embodiments, R1 and R2 are each benzyl.
In some embodiments, R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -C(Ry)2-, -C(Ry)2C(Ry)2-, -C(Ry)2C(Ry)2C(Ry)2-, -C(Ry)2OC(Ry)2-, and -C(Ry)2NRyC(Ry)2-. In certain embodiments, R1 and R2 are taken together to form a ring fragment selected from the group consisting of: -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2-, and -CH2NRyCH2-. In some embodiments, R1 and R2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle. In some embodiments, an activating functional group is
Figure imgf000073_0001
. In certain embodiments, R1 and R2 are each independently an optionally substituted group selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; and 8-10- membered aryl. In some embodiments, R1 and R2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R1 and R2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-C14 carbocycle, optionally substituted C3-C14 heterocycle, optionally substituted C6-CiO aryl, and optionally substituted 5- to 10- membered heteroaryl. In some embodiments, R1 and R2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R1 and R2 is independently perfluoro. In some embodiments, each occurrence of R1 and R2 is independently -CF2CF3.
In some embodiments, an activating functional group is
Figure imgf000073_0002
. In certain embodiments, R1, R2, and R3 are each independently an optionally substituted group selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; and 8-
10-membered aryl. In certain embodiments, R1, R2, and R3 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R1 and R2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-C14 carbocycle, optionally substituted C3- C14 heterocycle, optionally substituted C6-CiO aryl, and optionally substituted 5- to 10- membered heteroaryl. In certain embodiments, R1, R2, and R3 are each independently an optionally substituted C1-6 aliphatic. In certain embodiments, R1, R2, and R3 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In certain embodiments, R1, R2, and R3 are each independently perfluoro. In some embodiments, R1, R2, and R3 are each independently -
CF2CF3. In some embodiments, an activating functional group is
1 2
Figure imgf000074_0001
, where R and R are as defined above.
In certain embodiments, R1 and R2 are each independently an optionally substituted group selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; and 8-10-membered aryl. In some embodiments, R1 and R2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R1 and R2 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-C14 carbocycle, optionally substituted C3-C14 heterocycle, optionally substituted C6-CiO aryl, and optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R1 and R2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R1 and R2 is independently perfluoro. In some embodiments, each occurrence of R1 and R2 is independently -CF2CF3.
In certain embodiments, X is any anion. In certain embodiments, X is a nucleophile. In some embodiments, X is a nucleophile capable of ring opening an epoxide. In certain embodiments, X is absent. In certain embodiments, X is a nucleophilic ligand. Exemplary nucleophilic ligands include, but are not limited to, -ORX, -SRX, -O(C=O)RX, -O(C=O)ORX, -O(C=O)N(RX)2, -N(RX)(C=O)RX, -NC, -CN, halo (e.g., -Br, -I, -Cl), -N3, -O(SO2)RX and -OPRX 3, wherein each Rx is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl. In certain embodiments, X is -O(C=O)RX, wherein Rx is selected from optionally substituted aliphatic, fluorinated aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, fluorinated aryl, and optionally substituted heteroaryl.
For example, in certain embodiments, X is -O(C=O)RX, wherein Rx is optionally substituted aliphatic. In certain embodiments, X is -O(C=O)RX, wherein Rx is optionally substituted alkyl and fluoroalkyl. In certain embodiments, X is -O(C=O)CH3 or -0(C=O)CF3.
Furthermore, in certain embodiments, X is -O(C=O)RX, wherein Rx is optionally substituted aryl, fluoroaryl, or heteroaryl. In certain embodiments, X is -O(C=O)RX, wherein Rx is optionally substituted aryl. In certain embodiments, X is -O(C=O)RX, wherein Rx is optionally substituted phenyl. In certain embodiments, X is -0(C=O)CeHs or -0(C=O)C6F5.
In certain embodiments, X is -ORX, wherein Rx is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.
For example, in certain embodiments, X is -ORX, wherein Rx is optionally substituted aryl. In certain embodiments, X is -ORX, wherein Rx is optionally substituted phenyl. In certain embodiments, X is -OC6H5 or -OC6H2(2,4-NO2).
In certain embodiments, X is halo. In certain embodiments, X is -Br. In certain embodiments, X is -Cl. In certain embodiments, X is -I.
In certain embodiments, X is -O(SO2)RX. In certain embodiments X is -OTs. In certain embodiments X is -OSO2Me. In certain embodiments X is -OSO2CFs. In some embodiments, X is a 2,4-dinitrophenolate anion.
Lc. Phosphorous-Containing Activating Groups
In some embodiments, activating functional groups Z are phosphorous containing groups. In certain embodiments, a phosphorous-containing functional group is chosen from the group consisting of: phosphines (-PRy2); Phosphine oxides -P(O)Ry2; phosphinites P(OR7)Ry2; phosphonites P(OR7)2Ry; phosphites P(OR7)3; phosphinates OP(OR7)Ry 2; phosphonates; OP(OR7)2Ry; phosphates -OP(OR7)3; phosponium salts ([-PRy3] ) where a phosphorous-containing functional group may be linked to a metal complex through any available position (e.g. direct linkage via the phosphorous atom, or in some cases via an oxygen atom).
In certain embodiments, a phosphorous-containing functional group is chosen from the group consisting of:
Figure imgf000076_0001
or a combination of two or more of these
wherein R1 and R2, are as defined above; and
each R7 , is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C1--20 acyl; C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and where two R7 groups can be taken together with intervening atoms to form an optionally substituted ring optionally containing one or more heteroatoms, and an R7 group can be taken with an R1 or R2 group to an optionally substituted ring;
In some embodiments, phosphorous containing functional groups include those disclosed in The Chemistry of Organophosphorus Compounds. Volume 4. Ter- and Quinquevalent Phosphorus Acids and their Derivatives. The Chemistry of Functional Group Series Edited by Frank R. Hartley (Cranfield University, Cranfield, U.K.). Wiley: New York. 1996. ISBN 0-471-95706-2, the entirety of which is hereby incorporated herein by reference.
*— (X)b-[(R6R7R8P)+]n Qn-, wherein:
X is -O-, -N=, or -NRz-,
b is 1 or 0,
each of R6, R7 and R8 are independently present or absent and, if present, are independently selected from the group consisting of optionally substituted C1-C20 aliphatic, optionally substituted phenyl, optionally substituted C8-C14 aryl, optionally substituted 3- to 14-membered heterocyclic, optionally substituted 5- to 14-membered heteroaryl, halogen, =0, -ORZ, =NRZ, and N(RZ)2 where Rz is hydrogen, or an optionally substituted C1-C20 aliphatic, optionally substituted phenyl, optionally substituted 8- to 14-membered aryl, optionally substituted 3- to
14-membered heterocyclic, or optionally substituted 5- to 14-membered heteroaryl,
Q is any anion, and
n is an integer between 1 and 4. In some embodiments, an activating functional group is a phosphonate group:
Figure imgf000078_0001
, wherein R1, R2, and R7 is as defined above.
In specific embodiments, a phosphonate activating functional group is selected from the group consisting of:
Figure imgf000078_0002
In some embodiments, an activating functional group is a phosphonic diamide
group:
Figure imgf000078_0003
, wherein R1, R2, and R7 , are as defined above. In certain embodiments, each R1 and R2 group in a phosphonic diamide is methyl.
In some embodiments, an activating functional group is a phosphine group:
Figure imgf000078_0004
wherein R1, and R2 are as defined above.
In specific embodiments, a phosphine activating functional group is selected from the group consisting of:
Figure imgf000079_0001
Figure imgf000079_0002
//. Linker Moieties
As described above, each activating moiety (Z)m comprises a linker
Figure imgf000079_0004
Figure imgf000079_0003
coupled to at least one activating functional group Z as described above, with m denoting the number of activating functional groups present on a single linker moiety.
As noted above there may be one or more activating moiety
Figure imgf000079_0005
(Z)m tethered to a given metal complex, similarly, each activating moiety itself may contain more than one activating functional group Z. In certain embodiments, each activating moiety contains only one activating functional group (i.e. m = 1). In some embodiments, each activating moiety contains more than one activating functional groups (i.e. m > 1). In certian embodiments, an activating moiety contains two activating functional groups (i.e. m = 2). In certain embodiments, an activating moiety contains three activating functional groups (i.e. m = 3). In certain embodiments, an activating moiety contains four activating functional groups (i.e. m = 4). In certain embodiments where more than one activating functional group is present on an activating moiety, they are all the same functional group. In some embodiments where more than one activating functional group is present on an activating moiety, two or more of the activating functional groups are different. In certain embodiments, each linker moiety contains 1-30 atoms including
Figure imgf000080_0001
at least one carbon atom, and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.
In certain embodiments, the linker is an optionally substituted C2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by
-NRy-, -N(Ry)C(O)-, -C(O)N(R5)-, -O-, -C(O)-, -OC(O)-, -C(O)O-, -S-, -SO-, -SO2-, -C(=S)-, -C(=NRy)-, or -N=N-, where each occurrence of Ry is independently -H, or an optionally substituted radical selected from the group consisting of C1-6 aliphatic 3- to 7- membered heterocyclic, phenyl, and 8- to 10- membered aryl. In certain embodiments, a linker moiety is a C4-C12 aliphatic group substituted with one or more moieties selected from the group consisting of halogen, -NO2, -CN, -SRy, -S(O)Ry, -S(O)2Ry, -NRyC(0)Ry, -OC(O)Ry, -CO2Ry, -NCO, -N3, -OR7, -0C(0)N(Ry)2, -N(Ry)2, -NRyC(0)Ry, and -NRyC(0)0Ry, where Ry is -H, or an optionally substituted radical selected from the group consisting of Ci-6 aliphatic 3- to 7-membered heterocyclic, phenyl, and 8- to 10- membered aryl.
In certain embodiments, a linker moiety is an optionally substituted C3_C3o aliphatic group. In certain embodiments, a linker is an optionally substituted C4-24 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C4- C20 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C4-C12 aliphatic group. In certain embodiments, a linker is an optionally substituted C4_io aliphatic group. In certain embodiments, a linker is an optionally substituted C4-8 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C4-C6 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C6-C12 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted Cs aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C7 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C6 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C5 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C4 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C3 aliphatic group. In certain embodiments, a aliphatic group in the linker moiety is an optionally substituted straight alkyl chain. In certain embodiments, the aliphatic group is an optionally substituted branched alkyl chain. In some embodiments, a linker moiety is a C4 to C20 alkyl group having one or more methylene groups replaced by -C(RaRb)- where Raand Rb are each, independently C1-C4 alkyl groups. In certain embodiments, a linker moiety consists of an aliphatic group having 4 to 30 carbons including one or more gem-dimethyl substituted carbon atoms.
In certain embodiments, a linker moiety includes one or more optionally substituted cyclic elements selected from the group consisting of saturated or partially unsaturated carbocyclic, aryl, heterocyclic, or heteroaryl. In certain embodiments, a linker moiety consists of the substituted cyclic element, in some embodiments the cyclic element is part of a linker with one or more non-ring heteroatoms or optionally substituted aliphatic groups comprising other parts of the linker moiety.
In some embodiments, a linker moiety is of sufficient length to allow one or more activating functional groups to be positioned near a metal atom of a metal complex. In certain embodiments, structural constraints are built into a linker moiety to control the disposition and orientation of one or more activating functional groups near a metal center of a metal complex. In certain embodiments such structural constraints are selected from the group consisting of cyclic moieties, bicyclic moieties, bridged cyclic moieties and tricyclic moieties. In some embodiments, such structural constraints are the result of acyclic steric interactions. In certain embodiments such structural constraints are selected from the group consisting of cis double bonds, trans double bonds, cis allenes, trans allenes, and triple bonds. In some embodiments, such structural constraints are selected from the group consisting of substituted carbons including geminally disubstituted groups such as sprirocyclic rings, gem dimethyl groups, gem diethyl groups and gem diphenyl groups. In certain embodiments such structural constraints are selected from the group consisting of heteratom-containing functional groups such as sulfoxides, amides, and oximes.
In certain embodiments, linker moieties are selected from the group consisting of:
Figure imgf000082_0001
where s = 0-6 and t = 1-4
Figure imgf000082_0002
where * represents the site of attachment to a ligand, and each # represents a site of attachment of an activating functional group. In some embodiments, s is 0. In some embodiments, s is 1. In some embodiments, s is 2. In some embodiments, s is 3. In some embodiments, s is 4. In some embodiments, s is 5. In some embodiments, s is 6.
In some embodiments, t is 1. In some embodiments, t is 2. In some embodiments, t is 3. In some embodiments, t is 4.
///. Metal Complexes
As noted above, the present invention encompasses metal complexes that include a metal atom coordinated to a multidentate ligand and at least one activating moiety tethered to a multidentate ligand. In certain embodiments, provided metal complexes have the structure:
Figure imgf000083_0001
where
Figure imgf000083_0002
represents a metal atom coordinated to a multidentate ligand.
HLa. Metal Atoms
In certain embodiments, M is a metal atom selected from periodic table groups 3-
13, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 5-12, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 4-11, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 5-10, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 7-9, inclusive. In some embodiments, M is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni. In some embodiments, M is a metal atom selected from the group consisting of: cobalt; chromium; aluminum; titanium; ruthenium, and manganese. In some embodiments, M is cobalt. In some embodiments, M is chromium. In some embodiments, M is aluminum.
In certain embodiments, a metal complex is a zinc, cobalt, chromium, aluminum, titanium, ruthenium, or manganese complex. In certain embodiments, a metal complex is an aluminum complex. In some embodiments, a metal complex is a chromium complex.
In some embodiments, a metal complex is a zinc complex. In certain some embodiments, a metal complex is a titanium complex. In some embodiments, a metal complex is a ruthenium complex. In certain embodiments, a metal complex is a manganese complex. In certain embodiments, a metal complex is cobalt complex. In certain embodiments where the metal complex is a cobalt complex, the cobalt metal has an oxidation state of 3+ (i.e., Co(III)). In some embodiments, the cobalt metal has an oxidation state of 2+.
HLb. Ligands
In some embodiments, a metal complex
Figure imgf000084_0001
comprises a metal atom coordinated to a single tetradentate ligand and in some embodiments, the metal complex comprises a chelate containing a plurality of individual ligands. In certain embodiments, a metal complex contains two bidentate ligands. In some embodiments, a metal complex contains a tridentate ligand.
In various embodiments, tetradentate ligands suitable for metal complexes of the present invention may include, but are not limited to: salen derivatives 1, derivatives of salan ligands 2, bis-2-hydroxybenzamido derivatives 3, derivatives of the Trost ligand 4, porphyrin derivatives 5, derivatives of tetrabenzoporphyrin ligands 6, derivatives of corrole ligands 7, phthalocyaninate derivatives 8, and dibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives 9 or 9'.
Figure imgf000085_0001
In some embodiments, a metal multidentate ligand coordinated with a metal complex may comprise a plurality of discrete ligands. In some embodiments, metal complexes include two bidentate ligands. In certain embodiments, such bidentate ligands may have the structure
Figure imgf000086_0006
where Rd and R1 are as defined above. Metal complexes having two such ligands may adopt one of several geometries, and the present disclosure encompasses such variations.
In certain embodiments, metal complexes including two bidentate ligands may have structures selected from the group consisting of:
Figure imgf000086_0001
M
Figure imgf000086_0002
Figure imgf000086_0004
where each represents a ligand: [
Figure imgf000086_0005
Figure imgf000086_0003
In certain embodiments, a tetradentate ligand is a salen ligand. In certain embodiments, a metal complex is a metallosalenate. In certain embodiments, a metal complex is a cobalt salen complex. In certain embodiments, a metal complex is a chromium salen complex. In some embodiments, a metal complex is an aluminum salen complex.
In certain embodiments, at least one activating moiety is tethered to a carbon atom of a phenyl ring of the salicylaldehy de-derived portions of a salen ligand. In certain embodiments, at least one activating moiety is tethered to a carbon atom of a porphyrin ligand. In certain embodiments, at least one activating moiety is tethered to a pyrrole- carbon atom of a porphyrin ligand. In certain embodiments, at least one activating moiety is tethered to a carbon atom forming the bridge between the pyrrole rings of a porphyrin ligand. In certain embodiments, at least one activating moiety is tethered to one or more carbon atoms of only one phenyl ring of the salicylaldehy de-derived portions of a salen ligand, as shown in formula I:
Figure imgf000087_0001
wherein:
M is a metal atom;
X is a nucleophile capable of ring opening an epoxide;
k is an integer from 0-2 inclusive;
R' represents one or more substituents optionally present on the phenyl rings and each R' is independently selected from the group consisting of: halogen, -NO2, -CN, -SRy, -S(O)Ry, -S(O)2Ry, -NRyC(O)Ry, -OC(O)Ry, -CO2Ry, -NCO, -N3, -OR7, -OC(O)N(Ry)2, -N(Ry)2, -NRyC(O)Ry, -NRyC(O)ORy; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where two or more adjacent R groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;
Ry is -H, or an optionally substituted radical selected from the group consisting of Ci-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10- membered aryl;
represents is an optionally substituted moiety linking the two nitrogen
Figure imgf000088_0001
atoms of the diamine portion of the salen ligand, where
Figure imgf000088_0002
is selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an optionally substituted C2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by -NRy-, -N(Ry)C(O)-, -C(O)N(R5)-, -OC(O)N(R5)-, -N(Ry)C(O)O-, -OC(O)O-,
-O-, -C(O)-, -OC(O)-, -C(O)O-, -S-, -SO-, -SO2-, -C(=S)-, -C(=NRy)-, -C(=NORy)-or -N=N-;
represents one or more activating moieties, where is a
Figure imgf000088_0003
Figure imgf000088_0004
covalent linker containing one or more atoms selected from the group consisting of C, O, N, S, and Si; Z is a activating functional group and m is an integer from 1 to 4 indicating the number of individual activating functional groups present in each activating moiety.
In certain embodiments, both salicylaldehyde-derived portions of a salen ligand bear one or more activating moieties:
Figure imgf000089_0001
wherein M, X, k, R', and are as defined above.
Figure imgf000089_0004
Figure imgf000089_0005
In some embodiments, provided metal complexes comprise a
Figure imgf000089_0002
moiety that has the structure:
Figure imgf000089_0003
wherein:
M is a metal atom,
Rla, Rla', R2a, R2a', R3a, and R3a' are independently a (Z)m group, hydrogen,
Figure imgf000089_0006
halogen, -OR, -NR2, -SR, -CN, -NO2, -SO2R, -SOR, -SO2NR2; -CNO, -NRSO2R, -NCO, -N3, -SiR3; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; each R is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; carbamoyl; arylalkyl; phenyl, 8- to 10-membered aryl; C1-12 aliphatic; C1-12 heteroaliphatic; 5- to 10-membered heteroaryl; 4- to 7- memberedheterocyclyl; an oxygen protecting group; and a nitrogen protecting group; or:
two R on the same nitrogen atom are taken with the nitrogen to form a 3- to 7-membered heterocyclic ring;
wherein any of [R2a' and R3a'], [R2a and R3a], [Rla and R2a], and [Rla' and R2a'] may optionally be taken together with the carbon atoms to which they are attached to form one or more rings which may in turn be substituted with one or more
R20a groups; and
R4a is selected from the group consisting of:
Figure imgf000090_0001
d) , where
Rc at each occurrence is independently a
Figure imgf000090_0002
Z group, hydrogen, halogen,
-OR, -NR2, -SR, -CN, -NO2, -SO2R, -SOR, -SO2NR2; -CNO, -NRSO2R, -NCO, -N3, -SiR3; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to
8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; where: two or more Rc groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more rings; when two Rc groups are attached to the same carbon atom, they may be taken together along with the carbon atom to which they are attached to form a moiety selected from the group consisting of: a 3- to 8-memberedspirocyclic ring, a carbonyl, an oxime, a hydrazone, an imine;
X is a nucleophile capable of ring opening an epoxide;
Y is a divalent linker selected from the group consisting of: -NR-, -N(R)C(O)-, -C(O)NR-, -O-, -C(O)-, -OC(O)-, -C(O)O-, -S-, -SO-, -SO2-, -C(=S)-,
-C(=NR)-, or -N=N-; a polyether; a C3 to Cg substituted or unsubstituted carbocycle; and a Ci to Cg substituted or unsubstituted heterocycle; m ' is 0 or an integer from 1 to 4, inclusive; q is 0 or an integer from 1 to 4, inclusive; and x is 0, 1, or 2.
In some embodiments, at least one of [R2a and R3a] and [R2a and R3a ] are taken together to form a ring. In some embodiments, both [R2a and R3a] and [R2a and R3a ] are taken together to form rings. In some embodiments, the rings formed by [R2a and R3a] and [R2a and R3a ] are substituted phenyl rings. In certain embodiments, one or more of Rla, Rla , R2a, R2a , R3a, and R3a' are independently a
Figure imgf000092_0003
Z group.
In certain embodiments of provided metal complexes, a
Figure imgf000092_0001
moiety has a structure selected from the group consisting of:
Figure imgf000092_0002
wherein:
M is a metal atom;
R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a' are each independently a — ~w z group, hydrogen, halogen, -OR, -NR2, -SR, -CN, -NO2, -SO2R, -SOR, -SO2NR2; -CNO, -NRSO2R, -NCO, -N3, -SiR3; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein [Rla and R4a], [Rla' and R4a'] and any two adjacent R4a, R4a', R5a, R5a', R6a, R6a , R7a, and R7a groups can be taken together with intervening atoms to form one or more optionally substituted rings; n is 0 or an integer from 1 to 8, inclusive; and p is 0 or an integer from 1 to 4, inclusive. In some embodiments, M is Co. In some embodiments, Rla, Rla', R4a, R4a', R6a, and R6a' are each -H. In some embodiments, R5a, R5a , R7a and R7a are each optionally substituted C1-C12 aliphatic. In some embodiments, R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a' are each independently selected from the group consisting of: -H, -SiR3; methyl, ethyl, n-propyl, /-propyl, n-butyl, sec -butyl, /-butyl, isoamyl, /-amyl, thexyl, and trityl. In some embodiments, Rla, Rla , R4a, R4a , R6a, and R6a' are each -H. In some embodiments, R7a is selected from the group consisting of -H; methyl; ethyl; n-propyl; /-propyl; n-butyl; sec-butyl; /-butyl; isoamyl; /-amyl; thexyl; and trityl. In some embodiments, R5a and R7a are independently selected from the group consisting of -H; methyl; ethyl; n-propyl; /-propyl; n-butyl; sec-butyl; /-butyl; isoamyl; /-amyl; thexyl; and trityl. In certain embodiments, one or more of R5a, R5a , R7a and R7a' is a — group. In some embodiments, R5a and R5a'
Figure imgf000093_0002
are a Z group.
Figure imgf000093_0003
In certain embodiments of provided metal complexes, a
Figure imgf000093_0001
moiety has a structure selected from the group consisting of:
Figure imgf000094_0001
; and
In certain embodiments of complexes having formulae described above, at least one of the phenyl rings comprising a salicylaldehy de-derived portion of a catalyst is independently selected from the group consisting of:
Figure imgf000094_0002
Figure imgf000095_0001
where
Figure imgf000095_0003
^ (Z)m represents one or more independently-defined activating moieties which may be bonded to any one or more unsubstituted positions of a salicylaldehyde-derived phenyl ring.
In certain embodiments, there is an activating moiety tethered to the position ortho to a metal-bound oxygen substituent of one or both of the salicylaldehyde-derived phenyl rings of a salen ligand as in formulae 1Ha and 1Hb:
Figure imgf000095_0002
wherein:
M, X, k, R', and (Z)m are as defined above, and
Figure imgf000095_0004
Figure imgf000095_0005
R ) 44aa, r R> 44aa' , r R> 5Daa, r R> 5Daa' , R > 6oaa, and Roa are each independently a - Z group, hydrogen, halogen, -OR, -NR2, -SR, -CN, -NO2, -SO2R, -SOR, -SO2NR2; -CNO, -NRSO2R, -NCO, -N3, -SiR3; or an optionally substituted radical selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to
12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two adjacent R4a, R4a', R5a, R5a', R6a, and R6a' groups can be taken together with intervening atoms to form one or more optionally substituted rings.
In certain embodiments of compounds having formulae 1Ha or 1Hb, R4a, R4a , R6a, and R6a are each hydrogen, and R5a, R5a are, independently, optionally substituted C1-C20 aliphatic.
In certain embodiments of complexes 1Ha and 1Hb, at least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:
Figure imgf000096_0001
Figure imgf000097_0001
In certain embodiments, there is an activating moiety tethered to the position para to the phenolic oxygen of one or both of a salicylaldehy de-derived phenyl rings of the salen ligand as in structures IVa and IVb:
Figure imgf000097_0002
where M, X, k, R', R4a, R4a', R6a, R6a', R7a, R7a' ,
Figure imgf000097_0004
* , and (Z)m are as defined above.
Figure imgf000097_0005
In certain embodiments of compounds having formulae IVa or IVb, R4a, R4a , R6a, and R6a are hydrogen, and each R7a, R7a is, independently, optionally substituted C1-C20 aliphatic.
In certain embodiments of catalysts IVa and IVb, at least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:
Figure imgf000097_0003
Figure imgf000098_0001
In some embodiments, there is an activating moiety tethered to the position para to the imine substituent of one or both of the salicylaldehy de-derived phenyl rings of a salen ligand as in formulae Va or Vb:
w
Figure imgf000098_0002
here M, X, k, R', R4a, R4a', R5a, R5a', R7a, R7a', and (T)1n are as defined above.
In certain embodiments of compounds having formulae Va or Vb, each R and
R4a is h yyddrrooggeenn,, aanndd eeaacchh RR55a, R5a , R7a, R7a is, independently, hydrogen or optionally substituted C1-C20 aliphatic.
In certain embodiments of catalysts Va and Vb, at least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:
Figure imgf000098_0003
Figure imgf000099_0001
In some embodiments, there is an activating moiety tethered to the position ortho to the imine substituent of one or both of the salicylaldehy de-derived phenyl rings of a salen ligand as in formulae Via and VIb:
Figure imgf000100_0001
, where X, k,
M, R', R5a, R5a', R6a, R6a', R7a, R7a',
Figure imgf000100_0003
and (Z)m are as defined above.
In certain embodiments of compounds having formulae Via or VIb, each R6a and R6a is hydrogen, and each R5a, R5a, R7a, and R7a is, independently, hydrogen or optionally substituted C1-C20 aliphatic.
In certain embodiments of catalysts Via and VIb, at least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:
Figure imgf000100_0002
Figure imgf000101_0001
In some embodiments, there are activating moieties tethered to the positions ortho and para to the phenolic oxygen of one or both of the salicylaldehy de-derived phenyl rings of a salen ligand as in formulae Vila and VIIb:
Figure imgf000101_0002
where M, X, k, R', R4a, T R4a', R6a, R6a',
Figure imgf000101_0003
and
Figure imgf000101_0004
(Z)m are as defined above.
In certain embodiments of compounds having formulae Via or VIb, each R i 6aa, R6a, R4a, and R4a is, independently, hydrogen or optionally substituted C1-C20 aliphatic.
In certain embodiments of compounds having formulae Vila or VIIb, each R a,
R6a', R4a, and R4a' is hydrogen.
In some embodiments, there are activating moieties tethered to the positions ortho and para to the imine substituent of one or both of the salicylaldehy de-derived phenyl rings of a salen ligand as in formulae Villa and VIIIb:
Figure imgf000102_0001
or
where X, k, M, R', R5a, R5a', R7a, R7a', and — (Z)m are as defined above.
Figure imgf000102_0003
Figure imgf000102_0004
In certain embodiments of compounds having formulae Villa or VIIIb, each R5a, R5a, R7a, and R7a is, independently, optionally, hydrogen or substituted C1-C20 aliphatic.
In certain embodiments of the present invention, catalysts of structures Villa or VIIIb above, at least one of the phenyl rings comprising the salicylaldehy de-derived portion of a catalyst is independently selected from the group consisting of:
Figure imgf000102_0002
Figure imgf000103_0001
In some embodiments, there is an activating moiety tethered to the imine carbon n ligand as in formulae IXa and IXb:
Figure imgf000104_0001
where
M, X, k, R4a, R4a', R5a, R5a', R6a, R6a', R7a, R7a',
Figure imgf000104_0003
, and
Figure imgf000104_0004
(Z)m are as defined above with the proviso that the atom of the activating moiety attached to the salen ligand is a carbon atom.
In certain embodiments of compounds having formulae IXa or IXb, each R4a, R4a', R6a, and R6a' is hydrogen, and each R5a, R5a', R7a, and R7a' is, independently, hydrogen or optionally substituted C1-C20 aliphatic.
In certain embodiments of the present invention, metal complexes of structures IXa or IXb above, at least one of the phenyl rings comprising a salicylaldehy de-derived portion of a catalyst is independently selected from the group consisting of:
Figure imgf000104_0002
Figure imgf000105_0001
As shown above, the two phenyl rings derived from salicylaldehyde in the core salen structures need not be the same. Though not explicitly shown in formulae Ia through IXb above, it is to be understood that a catalyst may have an activating moiety attached to different positions on each of the two rings, and such compounds are specifically encompassed within the scope of the present invention. Furthermore, activating moieties can be present on multiple parts of the ligand, for instance activating moieties can be present on the diamine bridge and on one or both phenyl rings in the same catalyst. In certain embodiments, the salen ligand cores of catalysts Ia through IXb above are selected from the group shown below wherein any available position may be independently substituted with one or more R-groups or one or more activating moieties as described above.
Figure imgf000106_0001
and
where M, X, and k, are as defined above.
In some embodiments, at least one activating moiety is tethered to the diamine-derived portion of the salen ligand, as shown in formula X:
Figure imgf000106_0002
X , where M, X, k, R',
Figure imgf000106_0003
, and (Z)m are as
Figure imgf000106_0004
defined above.
In certain embodiments, salen ligands of formula X are selected from an optionally substituted moiety consisting of:
Figure imgf000107_0001
Figure imgf000107_0002
,where M, X, k, R', and
Figure imgf000107_0004
(Z) m are as defined above.
In certain embodiments, the diamine bridge of catalysts of formula Xa an optionally substituted moiety selected from the group consisting of:
Figure imgf000107_0003
Figure imgf000108_0001
, where M and ( (Z)m is as defined
Figure imgf000108_0002
above.
In certain embodiments, metallosalenate complexes of the present invention include, but are not limited to those in Table 1 below:
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
118
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
In certain embodiments, for complexes of Table 1, M is Co-X, where X is as defined above. In certain embodiments, for complexes of Table 1, M is Co-OC(O)CFs. In certain embodiments, for complexes of Table 1, M is Co-OAc. In certain embodiments, for complexes of Table 1, M is Co-OC(O)CeF5. In certain embodiments, for complexes of Table 1, M is C0-N3. In certain embodiments, for complexes of Table
1, M is Co-Cl. In certain embodiments, for complexes of Table 1, M is Co-nitrophenoxy. In certain embodiments, for complexes of Table 1, M is Co-dinitrophenoxy.
In some embodiments, for complexes of Table 1, M is Cr-X, where X is as defined above.
In certain embodiments, a tetradentate ligand is a porphyrin ligand. In some embodiments, a metal complex is a cobalt porphyrin complex. In certain embodiments, a metal complex is a chromium porphyrin complex. In some embodiments, a metal complex is an aluminum porphyrin complex.
Examples of porphyrin containing metal complexes of the present invention include, but are not limited to:
Figure imgf000123_0001
wherein each of M, X, k, R', and
Figure imgf000123_0002
(Z)m is as defined above.
In certain embodiments, a multidentate ligand is an optionally substituted tetrabenzoporphyrin. Suitable examples include, but are not limited to:
Figure imgf000124_0001
wherein M, R', and
Figure imgf000124_0002
(Z)n are as previously defined.
In certain embodiments of porphyrin and phthalocyanine -based complexes described herein, M is aluminum. In certain embodiments of porphyrin and phthalocyanine -based complexes described herein, M is cobalt. In certain embodiments of porphyrin and phthalocyanine-based complexes described herein, M is manganese.
In certain embodiments, porphyrin complexes of the present invention include, but are not limited to those in Table 2 below:
Figure imgf000125_0001
Figure imgf000126_0001

Figure imgf000127_0001
In certain embodiments, for complexes of Table 2, M is Co-X, where X is as defined above. In certain embodiments, for complexes of Table 2, M is Co-OC(O)CF3. In certain embodiments, for complexes of Table 2, M is Co-OAc. In certain embodiments, for complexes of Table 1, M is Co-OC(O)C6F5. In certain embodiments, for complexes of Table 2, M is C0-N3. In certain embodiments, for complexes of Table
2, M is Co-C1. In certain embodiments, for complexes of Table 2, M is Co-nitrophenoxy. In certain embodiments, for complexes of Table 2, M is Co-dinitrophenoxy.
In certain embodiments, for complexes of Table 2, M is Al-X, where X is as defined above. In certain embodiments, for complexes of Table 2, M is Cr-X, where X is as defined above.
In certain embodiments, porphyrin complexes of the present invention are synthesized as shown in the following schemes:
Figure imgf000129_0001
Figure imgf000130_0001
In some embodiments, the present disclosure provides methods of polymerization comprising contacting an epoxide with carbon dioxide in the presence of a provided metal complex to form a polycarbonate. In some embodiments, the present invention provides a method of polymerization, the method comprising:
a) providing an epoxide of formula:
Figure imgf000130_0002
wherein:
Ra is hydrogen or an optionally substituted radical selected from the group consisting of C1-3o aliphatic; C1-3o heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and
each of Rb , Rc , and Rd is independently hydrogen or an optionally substituted radical selected from the group consisting of C1-12 aliphatic; C1-12 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
wherein any of (Ra and Rc ), (Rc and Rd ), and (Ra and Rb ) can be taken together with intervening atoms to form one or more optionally substituted rings; ontacting the epoxide and carbon dioxide in the presence of a metal complex as described herein to provide a polymer having a formula selected from the group consisting of:
Figure imgf000132_0001
In some embodiments, a provided polymer has a formula:
Figure imgf000132_0002
In some embodiments, a provided polymer has a
formula: In some embodiments, carbon dioxide is optional
and a provided polymer has a formula:
Figure imgf000132_0004
In certain embodiments, Rb , Rc , and Rd are each hydrogen. In some embodiments, Ra is optionally substituted C1-i2 aliphatic. In some embodiments, Ra is optionally substituted C1-i2 heteroaliphatic . In some embodiments, the epoxide is ethylene oxide, propylene oxide, or cyclohexene oxide.
In certain embodiments, one of Ra , Rb , Rc , and Rd is hydrogen. In certain embodiments, two of Ra , Rb , Rc , and Rd are hydrogen. In certain embodiments, three of Ra', Rb', Rc', and Rd' are hydrogen. In certain embodiments, Ra is hydrogen. In certain embodiments, Rb is hydrogen. In certain embodiments, Rc is hydrogen. In certain embodiments, Rd is hydrogen.
In certain embodiments, Ra , Rb , Rc , and Rd are each independently an optionally substituted C1-3o aliphatic group. In certain embodiments, Ra , Rb , Rc , and Rd are each independently an optionally substituted C1--20 aliphatic group. In certain embodiments,
Ra , Rb , Rc , and Rd are each independently an optionally substituted C1-12 aliphatic group. In certain embodiments, Ra , Rb , Rc , and Rd are each independently an optionally substituted C1-8 aliphatic group. In certain embodiments, Ra , Rb , Rc , and Rd are each independently an optionally substituted C3-8 aliphatic group. In certain embodiments, Ra ,
Rb , Rc , and Rd are each independently an optionally substituted C3-12 aliphatic group.
In certain embodiments, Ra is an optionally substituted C1-3o aliphatic group. In certain embodiments, Rb is an optionally substituted C1-3o aliphatic group. In certain embodiments, Rc is an optionally substituted C1-3o aliphatic group. In certain embodiments, Rd is an optionally substituted C1-3o aliphatic group.
In some embodiments, an Ra and an Rb attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an Ra and an Rb attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 3-8- membered carbocyclic rings. In some embodiments, an Ra and an Rb attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.
In some embodiments, an Ra and an Rb attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12- membered carbocyclic rings. In some embodiments, an Ra and an Rb attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an Ra and an Rb attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings. In certain embodiments, an Ra and an Rb attached to the same carbon are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an Ra and an Rb attached to the same carbon are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an Ra and an Rb attached to the same carbon are taken together to form an optionally substituted 5-7-membered carbocyclic ring.
In some embodiments, an Rb and an Rc attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an Rb and an Rc attached to adjacent carbons are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an Rb and an Rc attached to adjacent carbons are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.
In some embodiments, an Rb and an Rc attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12- membered carbocyclic rings. In some embodiments, an Rb and an Rc attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an Rb and an Rc attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings.
In certain embodiments, an Rb and an Rc attached to adjacent carbons are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an Rb and an Rc attached to adjacent carbons are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an Rb and an Rc attached to adjacent carbons are taken together to form an optionally substituted 5-7-membered carbocyclic ring.
In certain embodiments, the polymer comprises a copolymer of two different repeating units where Ra , Rb , and Rc of the two different repeating units are not all the same. In some embodiments, a polymer comprises a copolymer of three or more different repeating units wherein Ra , Rb , and Rc of each of the different repeating units are not all the same as Ra , Rb , and Rc of any of the other different repeating units. In some embodiments, a polymer is a random copolymer. In some embodiments, a polymer is a tapered copolymer.
In some embodiments, a polymer contains a metal complex as described herein. In some embodiments, a polymer comprises residue of a metal complex as described herein. In some embodiments, a polymer comprises a salt of an organic cation and X, wherein X is a nucleophile or counterion. In some embodiments, X is 2,4- dinitrophenolate anion.
In some embodiments, Ra is optionally substituted C1-12 aliphatic. In some embodiments, Ra is optionally substituted C1-12 heteroaliphatic. In some embodiments, Ra is optionally substituted phenyl. In some embodiments, Ra is optionally substituted 8- to 10-membered aryl. In some embodiments, Ra is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, Ra is optionally substituted 3- to 7-membered heterocyclic . In certain embodiments, Ra is selected from methyl, ethyl, propyl, butyl, vinyl,
allyl, phenyl, trifluoromethyl,
Figure imgf000135_0001
Figure imgf000135_0002
? or any two or more of the above. In certain embodiments, Ra is methyl. In certain embodiments, Ra is ethyl. In certain embodiments, Ra is propyl. In certain embodiments, Ra is butyl. In certain embodiments, Ra is vinyl. In certain embodiments, Ra is allyl. In certain embodiments, Ra is phenyl. In certain embodiments, Ra is trifluoromethyl. In certain embodiments,
Ra is
Figure imgf000135_0004
. In certain embodiments, Ra is
Figure imgf000135_0005
. In certain embodiments,
Ra is
Figure imgf000135_0003
. In certain embodiments, Ra' is
Figure imgf000136_0001
In certain embodiments, Ra' is
Figure imgf000136_0002
. In certain
embodiments, Ra is
Figure imgf000136_0003
In some embodiments, Rb is hydrogen. In some embodiments, Rb is optionally substituted C1-12 aliphatic. In some embodiments, Rb is optionally substituted C1-12 heteroaliphatic. In some embodiments, Rb is optionally substituted phenyl. In some embodiments, Rb is optionally substituted 8- to 10-membered aryl. In some embodiments, Rb is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, Rb is optionally substituted 3- to 7-membered heterocyclic .
In some embodiments, Rc is hydrogen. In some embodiments, Rc is optionally substituted C1-12 aliphatic. In some embodiments, Rc is optionally substituted C1-12 heteroaliphatic. In some embodiments, Rc is optionally substituted phenyl. In some embodiments, Rc is optionally substituted 8- to 10-membered aryl. In some embodiments, Rc is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, Rc is optionally substituted 3- to 7-membered heterocyclic .
In some embodiments, Ra and Rc are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3. C14 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted C8-C10 aryl, and optionally substituted 5- to 10- membered heteroaryl.
In some embodiments, Rb and Rc are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3- C14 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted C8-C10 aryl, and optionally substituted 5- to 10- membered heteroaryl. In some embodiments, Ra and Rb are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C3-
C14 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted C8-C10 aryl, and optionally substituted 5- to 10- membered heteroaryl.
In some embodiments, the invention includes methods for synthesizing polyethers from epoxides. Suitable methods of performing these reactions are disclosed in US Patent No. 7,399,822, the entire contents of which are hereby incorporated herein by reference.
In some embodiments, the invention includes methods for synthesizing cyclic carbonates from carbon dioxide and epoxides using catalysts described above, suitable methods of performing this reaction are disclosed in US Patent No. 6,870,004 which is incorporated herein by reference.
EXAMPLES
Example 1
A general route to a symmetric cobalt (III) salen ligand of the present invention is shown in Schemes El and E2, below:
Scheme El
Figure imgf000138_0001
As shown in Scheme El, disubstituted phenol El-a is formylated to provide salicylaldehyde derivative El-b. Two equivalents of this aldehyde are then reacted with a diamine (in this case 1,2-diamino cyclohexane) to afford Schiff base El-c. This compound is then reacted with cobalt (II) acetate to give the Co(II)-salen complex (not shown) which is oxidized by air in the presence of trifluoroacetic acid to afford the active cobalt (III) catalyst. Similar chemistries can be applied to synthesis of the catalysts described hereinabove. One skilled in the art of organic synthesis can adapt this chemistry as needed to provide the specific catalysts described herein.
Example 2
A typical route to an asymmetric cobalt (III) salen ligand is shown in Scheme E2: Scheme E2
Figure imgf000139_0001
As shown in Scheme E2, disubstituted salicylaldehyde derivative El-b is treated with one equivalent of a monohydrochloride salt of 1,2 cyclohexanediamine. the resulting Schiff base E2-a is then neutralized and a second different salicylaldehyde derivative is added. This compound is then reacted with cobalt (II) acetate to give the Co(II)-salen complex which is oxidized by air in the presence of trifluoroacetic acid to afford the active cobalt (III) catalyst. Similar chemistries can be applied to synthesis of the catalysts described hereinabove. One skilled in the art of organic synthesis can adapt this chemistry as needed to provide the specific catalysts described herein.
Example 3
Example 3 describes the synthesis of a catalyst
Figure imgf000139_0002
s where M is
Co(III),
Figure imgf000139_0003
is salcy,
Figure imgf000139_0004
is
Figure imgf000139_0005
, Z is a P-linked phosphorimine moiety , and m is 1, wherein there are one or two
Figure imgf000140_0002
groups present
Figure imgf000140_0003
(Scheme E4 and E3, respectively).
Scheme E3
Figure imgf000140_0001
As shown in Scheme E3, triol E3-a is protected as a ketal to afford monohydric alcohol E3-b, this compound is then alkylated with bromide E3-c to afford benzyl ether E3-d. Deprotection and oxidation of the other benzylic alcohol affords salicylaldehyde E3-e which is condensed with cyclohexanediamine as described above to give ligand E3- f. The phosphorimine nitrogen is then quaternized and the metal complex formed as before to provide catalyst E3-h. In an alternative route not shown here the metal is first inserted and then quarternization is performed.
Scheme E3b
Figure imgf000141_0001
As shown in Scheme E3b, salicyladedyde E3-e (described above) is condensed with cyclohexanediamine monohydrochloride to afford the mono-Schiff base hydrochloride E4a. This salt is then neutralized, condensed with di-t-butyl salicaldehyde, and methylated to give E4-b. The resulting ligand is metallated and oxidized as described above for Scheme E3 to give catalyst E4-c.
Example 4
Example 4 describes the synthesis of catalysts where M is Co(III),
Figure imgf000141_0002
is salcy,
Figure imgf000141_0003
is
Figure imgf000141_0004
, Z is a l-[4-dimethylamino-pyridinium]
Figure imgf000141_0005
or 1-[N- methylimidazolium],
Figure imgf000141_0006
and m is 1, wherein there are one or two ™ groups
Figure imgf000141_0007
present (Scheme E5 and E6, respectively). Scheme E4
Z' = N,N-dimethyla or N-methyl im
Figure imgf000142_0001
Scheme E4 shows the synthesis of compounds CS-6 and CS-7. For each compound trans- 1 ,2-Diaminocycloh.exane (2.0 mol) is slowly added to an anhydrous ethanol solution of benzyl chloride CS-4 (1.0 mol). The reaction is stirred and heated to reflux for 3 h, then cooled to rt and diluted with water. This mixture is cooled overnight in the freezer and solids are collected by filtration to afford dichloride CS-5. The dichloride CS-5 (1.0 mol) is reacted with N,N-Dimethylamino pyridine (2.0 mol) or N- methyl imidazole in acetonitrile. The reactions are heated at 80 °C for 18 h and then the solvent is removed in vacuo to provide the respective ammonium salts. These salts are metallated and oxidized as described previously to provide catalysts CS-6 and CS-7. Example 5
Example 5 describes the synthesis of catalysts where M is Co(III),
Figure imgf000143_0004
is salcy,
Figure imgf000143_0002
is
Figure imgf000143_0003
, Z is a l-[N-methylimidazolium] (CS-8), or dimethylamino (CS-9) and m is 1, wherein there are two
Figure imgf000143_0005
groups present (Scheme E5 and E6, respectively).
Scheme E5
Figure imgf000143_0001
Scheme E5 shows the synthesis of compounds CS-8 and CS-9 using conditions similar to those described above. Synthesis of CS-8: The known compound l-(2- methylaminoethyl)-3-methylimidazole (2.0 mol) is combined with CS-5 (1.0 mol) in acetonitrile. The reaction is heated to 80 °C for 18 h and then the solvent is removed in vacuo, metallation with Co(OAc)2 and oxidation in TFA are then performed as described above to afford catalyst CS-8. Synthesis of CS-9: N5N5N '-Trimethyl-1 ,2-ethanediamine (4.0 mol) is combined with CS-5 (1.0 mol) in acetonitrile. The reaction is heated to 80 °C for 18 h, cooled, and the solvent is removed in vacuo. The crude product is diluted with ether, filtered to remove amine salts, and concentrated in vacuo. The residue is dissolved in degassed methanol and combined with Co(OAc)2 (1.0 mol). After stirring for 3 h the residue is filtered and washed with methanol. Trifluoroacetic acid (1.0 mol) is added slowly to a stirring solution of the solid residue in dichloromethane. After stirring open to air for 3 h, the solids are filtered and dried in vacuo to produce CS-9. Example 6
Example 6 and Scheme E6 describe the synthesis of catalysts where M is Co(III),
Figure imgf000144_0002
is salcy,
Figure imgf000144_0009
is
Figure imgf000144_0003
, Z is dibutylamino and m is 1, wherein there are two groups present.
Figure imgf000144_0004
Scheme E6
Figure imgf000144_0001
Synthesis of CS-IO: Ligand CS-5 (1.0 mol), 3-(dibutylamino)-1-propanol (2.0 mol), a 50% NaOH solution (10 mol), tetrabutylammonium bisulphate (4 mol %), and dichloromethane are combined and heated at 65 °C overnight. The reaction mixture is concentrated in vacuo to remove the bulk of the solvent and the aqueous layer is extracted with ethyl acetate. The organic layer is separated, dried with magnesium sulfate, filtered, and concentrated in vacuo. After purification using silica gel the product is dissolved in degassed methanol and combined with Co(OAc)2 (1.0 mol). After stirring for 3 h, the residue is filtered and washed with methanol. Trifluoroacetic acid (1.0 mol) is added slowly to a dichloromethane solution of the solid residue. After stirring open to air for 3 h, the solids are filtered and dried in vacuo to produce CS-IO.
Example 7
Example 7 and Scheme E7 describe the synthesis of catalysts where M is Co(III),
Figure imgf000144_0005
is salcy, includes two groups taken together to form a ring
Figure imgf000144_0006
Figure imgf000144_0007
including the Z group, Z is 3-[N-methylpyridinium] and m is 1, wherein there is one
Figure imgf000144_0008
(Z)m group present. Scheme E7
Figure imgf000145_0001
Synthesis of CS-Il. Ligand CS-5 (1.0 mol), 3,5-bis(hydroxymethyl)-N- methylpyridinium iodide (2.0 mol), a 50% NaOH solution (10 mol), tetrabutylammonium bisulphate (4 mol %), and dichloromethane are combined and heated at 65 °C overnight. The reaction mixture is concentrated in vacuo to remove the bulk of the solvent and the aqueous layer is extracted with ethyl acetate. The organic layer is separated, dried with magnesium sulfate, filtered, and concentrated in vacuo. The procedure detailed above for the metallation and oxidation is followed to produce CS-Il.
Example 8
Example 8 and Scheme E8 describe the synthesis of catalysts where M is Co(III),
Figure imgf000145_0002
, Z is l-[4-t-butylpyridinium], and m is 2, wherein there are two
Figure imgf000145_0003
(Z)m groups present.
Scheme E8
Figure imgf000146_0001
Figure imgf000146_0002
Synthesis of AC-2. Intermediate AC-I (0.37 g, 0.35 mmol), 4-tbutylpyridine (0.21 rnL, 1.41 mmol), and AcCN (4 mL) were combined in a sealed vial and heated to 80 °C with stirring for 18 h. The solvent was removed in vacuo, leaving a yellow residue
(0.61 g, 110% yield, AcCN present). 1H NMR (400 MHz, CDCl3, δ): 9.53 (t, 8H), 8.21 (s, 2H), 7.94 (t, 8H), 7.08 (s, 2H), 6.83 (s, 2H), 4.81 (m, 8H), 3.29 (m, 2H), 2.78 (m, 2H), 2.15 (s, 6H), 1.5-2.0 (m, 24 H), 1.36 (s, 36H); IR (ATR, film cast from AcCN): vc=N = 1637 cm-1. A solution of the residue (0.30 g, 0.19 mmol) in dry EtOH (5 mL) was added to AgBF4 (0.19 g, 0.85 mmol) in a schlenk tube and stirred overnight shielded from the light. The solution was filtered through Celite and the solvent was removed in vacuo, giving a solid residue. This residue was flashed over a small plug of silica gel with 5:1 CH2Cl2:Et0H as eluant. The solvent was removed to give a solid residue (0.18 g, 67% yield). 1H NMR (400 MHz, CDCl3, δ): 8.75 (t, 8H), 7.98 (d, 2H), 7.92 (t, 8H), 7.1-7.3 (m, 4H), 4.52 (m, 8H), 3.6 (m, 2H), 2.7 (m, 2H), 2.19 (s, 6H), 1.5-2.0 (m, 24 H), 1.38 (s,
36H); IR (ATR, film cast from CH2Cl2): vc=N= 1641 cm-1, vBF4= 1050 cm-1. A solution of the residue (0.18 g, 0.12 mmol) in dry EtOH (4 mL) was added to Co(OAc)2 (0.022 g, 0.12 mmol) in a schlenk tube under N2. The solution was stirred for 3 h at room temperature, and the solvent was removed in vacuo. The residue was triturated with ether, dried in vacuo, and redissolved in CH2Cl2. A solution Of CF3CO2H (9 μL, 0.12 mmol) in CH2Cl2 (80 μL) was added and the solution stirred for 3 h open to air. Solid NaO2CCF3 (0.067 g, 0.49 mmol) was added, and the solution was stirred under N2 for 2 days. The solution was filtered through Celite and the solvent was removed in vacuo to leave a brown residue (0.071g, 37% yield). 1H NMR (400 MHz, DMSO-d6, δ): 8.86 (t, 8H), 8.08 (t, 8H), 8.07 (s, 2H), 7.30 (m, 4H), 4.44 (m, 8H), 3.54 (m, 2H), 2.9 (m, 2H), 2.47 (s, 6H), 1.5-2.0 (m, 24 H), 1.29(s, 36H); IR (ATR): vc=o = 1682 cm 1, VC=N = 1641 cm-1.
Additional ligands AC-6 through AC-I l were synthesized using the conditions described for compound AC-2 and are summarized in Scheme E8b and Table E8:
Scheme E8b
Figure imgf000148_0001
Figure imgf000148_0002
Example 9
Example 9 and Scheme E9 describe the synthesis of catalysts where M is Co(III),
Figure imgf000149_0002
is salcy,
Figure imgf000149_0004
is
Figure imgf000149_0003
, Z is N,N-bis-(3-dimethylaminopropyl)amino (AC-4), tetramethyl guanidino (AC-5), N-linked morpholino (AC-6), or N-linked piperidino (AC- 14), and m is 2, wherein there are two
Figure imgf000149_0005
(Z)m groups present.
Scheme E9
Figure imgf000149_0001
Synthesis of AC-4. Intermediate AC-3 (0.45 g, 0.63 mmol), 3,3'-iminobis(N,N'- dimethylpropylamine) (0.28 mL, 1.26 mmol), K2CO3 (0.35 g, 2.52 mmol) and AcCN (5 mL) were combined in a sealed vial and heated to 80 °C with stirring for 18 h. The solution was filtered and the solvent was removed in vacuo, triturated with ether, and dried in vacuo to leave a yellow residue (0.48 g, 91% yield). 1H NMR (400 MHz, CDCl3, δ): 8.21 (m, 2H), 6.8-7.2 (m, 4H), 3.75 (m, 2H), 3.0-3.4 (m, 20H), 2.0-2.8 (m, 28H), 2.18
(s, 6H), 1.4-2.0 (m, 24 H); IR (ATR): VC=N = 1600 cm-1. A solution of the residue (0.21 g, 0.25 mmol) in dry EtOH (10 mL) was added to Co(OAc)2 (0.045 g, 0.25 mmol) in a schlenk tube under N2. CH2Cl2 (3 mL) was added to completely dissolve the solution. The solution was stirred for 18 h at room temperature, and the solvent was removed in vacuo. The residue was triturated with ether, dried in vacuo, and redissolved in CH2Cl2 (10 mL). CF3CO2H (20 μL, 0.25 mmol) was added and the solution stirred for 3.5 h open to air. The solvent was removed in vacuo, triturated with ether, and dried in vacuo to leave a brown residue (0.28 g, 108% yield, residual CH2Cl2). 1H NMR (400 MHz, DMSO-de, δ): 7.92 (m, 2H), 7.1-7.4 (m, 4H), 3.58 (m, 2H), 3.0-3.4 (m, 20H), 2.0-2.8 (m, 28H), 2.3 (s, 6H), 1.4-2.0 (m, 24 H); IR (ATR): vc=o= 1688 cm-1, VC=N = 1616 cm-1.
Synthesis of AC-5. Intermediate AC-3 (0.20 g, 0.29 mmol), 1,1,3,3- tetramethylguanidine (0.21 mL, 1.71 mmol), K2CO3 (0.39 g, 2.85 mmol) and AcCN (2 mL) were combined in a sealed vial and reacted as in AC-4, except that the residue was also washed with hexanes. 1H NMR (400 MHz, CDCl3, δ): 8.23 (d, 2H), 6.95 (s, 2H),
6.80 (s, 2H), 3.35 (m, 2H), 3.1 (m, 4H), 2.7-2.8 (m, 24H), 2.48 (m, 4H), 2.20 (s, 6H), 1.4-
2.0 (m, 16 H); IR (ATR): VC=N = 1594 cm-1. The residue was reacted as in AC-4. IR (ATR): Vc=O = 1690 cm-1, vc=N= 1610 cm-1.
Synthesis of AC-6. Intermediate AC-3 (0.32 g, 0.44 mmol), morpholine (0.16 mL, 1.77 mmol), K2CO3 (0.61 g, 4.4 mmol) and AcCN (4 mL) were combined in a sealed vial and reacted as in AC-4, except that the residue was also washed with a NaOAc buffer (pH=4) solution to remove residual morpholine. 1H NMR (400 MHz, CDCl3, δ): 8.22 (s, 2H), 6.92 (s, 2H), 6.79 (s, 2H), 3.69 (m, 8H), 3.28 (m, 2H), 2.2-2.5 (m, 16H),
2.19 (s, 6H), 1.4-2.0 (m, 16 H). The residue was reacted as in AC-4. 1H NMR (400 MHz, DMSO-d6, δ): 7.91 (s, 2H), 7.23 (s, 2H), 7.14 (s, 2H), 3.6 (m, 2H), 3.52 (m, 8H), 2.99 (m, 2H), 2.57 (s, 6H), 2.47 (m, 4H), 2.2-2.5 (m, 12H), 1.4-2.0 (m, 16 H); IR (ATR): vc=o = 1671 cm-1, Vc=N= 1630 cm-1.
Additional ligands AC- 13 and AC- 14 were synthesized using the conditions described for compounds AC-4 through AC-6 and are summarized in Scheme E9b and Table E9:
Scheme E9b
Figure imgf000151_0001
Figure imgf000151_0002
Example 10
Confirmation of inventive concepts, processes, methods, and compositions described herein has been provided, among other ways, through publication by others after the priority date of the present case. For example, Examples 10-27 describe working Examples presented in Chinese Patent Application No. 200810229276.1, published as CN 101412809A. Additional experimental and characterization data are described by Lu and co-workers, J. Am. Chem. Soc, 2009, 131, 11509-11518, and supporting information available at www.pubs.acs.org, the entirety each of which is hereby incorporated by reference.
In certain embodiments, provided catalysts and/or methods for the preparation of polycarbonate are characterized by one or more of the following: retaining high catalytic activity at low catalyst concentration; reaction conditions that are relatively mild; high catalytic activity with high selectivity for polymer product; alternate structure in the polycarbonate product higher than 97% with relatively narrow distribution of molecular weight; retaining high catalytic activity for copolymerization of carbon dioxide and epoxides at higher reaction temperatures (e.g., above 50 °C, above 75 °C, or above 100 °C); and catalysts that can be used to catalyze the polymerization of carbon dioxide with two or more alkylene oxides for the synthesis of polycarbonate polymer.
The following materials were added sequentially into a stainless steel high pressure reactor of effective volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex I-a (Ri is cyclohexyl diamine, X is NO3 -1 anion; R2=H; R3, R4 and R5 are tertiary butyl; group containing organic base group is at position 3 of the benzene ring in the ligand, n is 2) and one mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure is maintained constant at 2.0 MPa. The temperature was controlled at 25 °C. The content was stirred with a magnetic stirring bar for 6 hours and the remaining carbon dioxide was slowly released. The remaining alkylene oxide was collected in -20 °C cold trap and a certain amount of mixture of methanol/chloroform was added to dissolve the high polymer. Then a large amount of diethyl ether was added to precipitate the polycarbonate. The precipitate was filtered and washed several times with diethyl ether and dried in vacuum to constant weight to afford 27 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 101,000 g/mol with a molecular weight distribution of 1.24. A Varian INOVA-400MHz Nuclear Magnetic Resonance spectrometer was used to determine its 1H-NMR and the result showed that the alternate structure is over 99%.
Figure imgf000153_0001
I-a
Example 11
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the molar ratio of catalyst to propylene oxide was changed from 1 :10000 to 1 :50000 (0.02 mmole of catalyst and 1 mole of propylene oxide were used). The reaction was carried out at 25 °C for 24 hours to afford 21 grams of poly(propylene carbonate) with a molecular weight of 223,000 g/mol and a molecular weight distribution of 1.29. The polymer formed contained more than 99% carbonate linkages.
Example 12
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the molar ratio of catalyst to propylene oxide was changed from 1 :10000 to 1 :200000 (0.008 mmole of catalyst and 1.6 mole of propylene oxide were used). The reaction was carried out at 50 °C for 10 hours to afford 19 grams of poly(propylene carbonate) with a molecular weight of 318,000 g/mol and a molecular weight distribution of 1.37. The polymer formed contained more than 99% carbonate linkages.
Example 13
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the molar ratio of catalyst to propylene oxide was changed from 1 :10000 to 1 :2000 (0.5 mmole of catalyst and 1 mole of propylene oxide were used). The reaction was carried out at 25 °C for 3 hours to afford 48 grams of poly(propylene carbonate) with a molecular weight of 52,800 g/mol and a molecular weight distribution of 1.30. The polymer formed contained more than 99% carbonate linkages.
Example 14
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the reaction temperature was changed from 25 °C to 100 °C and the reaction was carried out for 0.5 hours to afford 34 grams of poly(propylene carbonate) with a molecular weight of 112,400 g/mol and a molecular weight distribution of 1.38. The polymer formed contained more than 99% carbonate linkages.
Example 15
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the reaction temperature was changed from 25 °C to 10 °C and the reaction was carried out for 10 hours to afford 18 grams of poly(propylene carbonate) with a molecular weight of 914,000 g/mol and a molecular weight distribution of 1.38. The polymer formed contained more than 99% carbonate linkages.
Example 16
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the propylene oxide was replaced with 1,2-butylene oxide. The reaction was carried out at 25 °C for 6 hours to afford 31 grams of poly(butylene carbonate) with a molecular weight of 127,000 g/mol and a molecular weight distribution of 1.21. The polymer formed contained more than
99% carbonate linkages. Example 17
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the propylene oxide was replaced with 1,2-octylene oxide. The reaction was carried out at 25 °C for 10 hours to afford 34 grams of poly(octylene carbonate) with a molecular weight of 109,000 g/mol and a molecular weight distribution of 1.38. The polymer formed contained more than 99% carbonate linkages.
Example 18
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the propylene oxide was replaced with a mixture of propylene oxide and cyclohexylene oxide (the molar ratio of the catalyst to propylene oxide and cyclohexylene oxide was 1 : 5000: 5000). The reaction was carried out at 50 °C for 6 hours to afford 59 grams of poly(propylene-co-cylcohexene carbonate) with a molecular weight of 187,000 g/mol and a molecular weight distribution of 1.29. The polymer formed contained more than 99% carbonate linkages.
Example 19
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the axial anion in the cobalt complex I-a was changed from nitrate radical to acetate moiety. The reaction was carried out at 25 °C for 6 hours to afford 34 grams of poly(propylene carbonate) with a molecular weight of 95,000 g/mol and a molecular weight distribution of 1.28. The polymer formed contained more than 99% carbonate linkages.
Example 20
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the diamine skeleton in the cobalt complex I-a was changed from cyclohexane diamine to ethylene diamine. The reaction was carried out at 25 °C for 6 hours to afford 29 grams of poly(propylene carbonate) with a molecular weight of 112,000 g/mol and a molecular weight distribution of 1.20. The polymer formed contained more than 99% carbonate linkages.
Example 21
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the diamine skeleton in the cobalt complex I-a was changed from cyclohexane diamine to o-phenylene diamine. The reaction was carried out at 25 °C for 6 hours to afford 25 grams of poly (propylene carbonate) with a molecular weight of 92,000 g/mol and a molecular weight distribution of 1.15. The polymer formed contained more than 99% carbonate linkages.
Example 22
The following materials were added sequentially into a stainless steel high pressure reactor of volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex I-b (Ri is 1 ,2-propylene diamine, X is dinitrophenyl anion; R2=H; Ri is tertiary butyl; there are organic base groups at position 5 of the two benzene rings in the ligand, n is 0) and 1 mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure was maintained constant at 2.0 MPa. The reaction was carried out at 25 °C for 6 hours to afford 23 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 81 ,000 g/mol with a molecular weight distribution of 1.34. The polymer formed contained more than 99% carbonate linkages.
Figure imgf000157_0001
Example 23
The following materials were added sequentially into a stainless steel high pressure reactor of volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex I-c (Ri is ethylene diamine, X is dinitrophenyl anion; R2=H; R3 is tertiary butyl; there are organic base groups at position 3 and position 5 of one of the benzene rings in the ligand, n is 0) and 1 mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure was maintained constant at 2.0 MPa. The reaction was carried out at 25 °C for 6 hours to afford 23 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 81,000 g/mol with a molecular weight distribution of 1.34. The polymer formed contained more than 99% carbonate linkages.
Figure imgf000157_0002
Example 24
The following materials are added sequentially into a stainless steel high pressure reactor of volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex I-b (Ri is ethylene diamine, X is dinitrophenyl anion; R2=H; R3 and R4 are tertiary butyl; there are organic base groups at position 5 of the two benzene rings in the ligand, n is 0) and 1 mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure was maintained constant at 2.0 MPa. The reaction was carried out at 25 °C for 6 hours to afford 26 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 83,000 g/mol with a molecular weight distribution of 1.19. The polymer formed contained more than 99% carbonate linkages. The polymer formed contained more than 99% carbonate linkages.
Example 25
The following materials are added sequentially onto a stainless steel high pressure reactor of volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex I-a
(Ri is 2,3-butylene diamine, X is nitrate anion; R2=H; R3 and R4 are methoxyl group; Ri is tertiary butyl; there is an organic base group at position 3 of one of the benzene rings in the ligand, n is 2) and 1 mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure is maintained constant at 2.0 MPa. The reaction was carried out at 25 °C for 6 hours to afford 22 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 73,000 g/mol with a molecular weight distribution of 1.14. The polymer formed contained more than 99% carbonate linkages.
Example 26
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the pressure was changed from 2.0 MPa to 0.1 MPa. The reaction was carried out at 25 °C for 10 hours to afford 25 grams of poly(propylene carbonate) with a molecular weight of 100,400 g/mol and a molecular weight distribution of 1.17. The polymer formed contained more than 99% carbonate linkages.
Example 27
The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the pressure was changed from 2.0 MPa to 6.0 MPa. The reaction was carried out at 25 °C for 6 hours to afford 29 grams of poly(propylene carbonate) with a molecular weight of 125,000 g/mol and a molecular weight distribution of 1.25. The polymer formed contained more than 99% carbonate linkages.
Figure imgf000160_0001
While we have described a number of embodiments of this invention, it is apparent that our basic examples may be altered to provide other embodiments that utilize the compounds and methods of this invention. Therefore, it will be appreciated that the scope of this invention is to be defined by the appended claims rather than by the specific embodiments that have been presented by way of example.

Claims

What is claimed is:
1. A method comprising the step of contacting an epoxide and carbon dioxide with a polymerization catalyst having the structure:
Figure imgf000162_0001
wherein:
M is a metal atom;
Figure imgf000162_0003
comprises a multidentate ligand; and
Figure imgf000162_0004
(Z)m represents one or more activating moieties tethered to the multidentate ligand, where
Figure imgf000162_0005
represents a linker moiety; m represents the number of Z groups present on a linker moiety and is an integer between 1 and 4 inclusive; and each (Z) is an activating functional group independently selected from the group consisting of:
Figure imgf000162_0002
Figure imgf000163_0001
Figure imgf000163_0002
wherein: each occurrence of R1, R2 and R3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly eye lie saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein two or more R1, R2 and R3 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms;
R4 is hydrogen, hydroxyl, optionally substituted C1--20 aliphatic;
each occurrence of R5 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1 -3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly eye lie saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein an R5 group can be taken with an R1 or R2 group to form one or more optionally substituted rings;
each occurrence of R7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C1--20 acyl; C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where an R7 group can be taken with an R5 group to form one or more optionally substituted rings optionally containing one or more heteroatoms;
each occurrence of R7 , is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C1--20 acyl; C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and where two R7 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, and an R7 group can be taken with an R1 or R2 group to form one or more optionally substituted rings optionally containing one or more heteroatoms; each occurrence of R8, R9, and R10 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1 -3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly eye lie saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more R8, R9 and R10 groups can be taken together with intervening atoms to form one or more optionally substituted rings;
each occurrence of R11 is independently selected from the group consisting of: halogen, -NO2, -CN, -SRy, -S(O)Ry, -S(O)2Ry, -NRyC(O)Ry, -OC(O)Ry, -CO2Ry, -NCO, -N3, -OR7, -OC(O)N(Ry)2, -N(Ry)2, -NRyC(0)Ry, -NRyC(0)0Ry; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle, a 7- 14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where each occurrence of Ry is independently selected from the group consisting of hydrogen an optionally substituted C1-6 aliphatic group, and an optionally substituted aryl group, where two or more adjacent R11 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;
X is an anion;
ring A is an optionally substituted 5- to 10-membered heteroaryl group having 0 to 4 additional heteroatoms independently selected from nitrogen, oxygen, or sulfur;
with the provisos that:
when Z is
Figure imgf000167_0001
, ring A is not an imidazole, an oxazole, or a thiazole; and
when
Figure imgf000167_0002
is
Figure imgf000167_0003
where
Figure imgf000167_0004
IS
-CH2- , Z is not
Figure imgf000167_0005
2. The method of claim 1, wherein M is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni.
3. The method of claim 1, wherein M is selected from the group consisting of: Co, Al, and Cr.
4. The method of claim 1 , wherein M is Co.
5. The method of claim 1 , wherein M is Cr.
6. The method of claim 1 , wherein M is Al.
7. The method of claim 1, wherein the moiety contains 1-30 atoms including
Figure imgf000168_0001
at least one carbon atom, and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.
8. The method of claim 1, wherein the moiety is a C2-30 aliphatic group
Figure imgf000168_0002
wherein one or more methylene units are optionally and independently replaced by -NRy-, -N(Ry)C(O)-, -C(O)N(R5)-, -O-, -C(O)-, -OC(O)-, -C(O)O-, -S-, -Si(Ry)2-, -SO-, -SO2-, -C(=S)-, -C(=NRy)-, or -N=N-, where each occurrence of Ry is independently -H, or an optionally substituted radical selected from the group consisting of C 1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10- membered aryl.
9. The method of claim 1, wherein the moiety is selected from the group consisting of:
Figure imgf000168_0003
Figure imgf000169_0001
Figure imgf000169_0002
Figure imgf000169_0003
Figure imgf000169_0004
Figure imgf000169_0006
Figure imgf000169_0005
Figure imgf000169_0007
where s = 0-6 and t = 1 -4
Figure imgf000169_0008
where * represents the site of attachment to the ligand, and each # represents a site of attachment of an activating functional group.
10. The method of claim 1, wherein the
Figure imgf000170_0002
^ moiety comprises a tetradentate ligand.
11. The method of claim 1 , wherein the
Figure imgf000170_0003
moiety comprises two bidentate ligands
12. The method of claim 10, wherein the tetradentate ligand is selected from the group consisting of salen derivatives, derivatives of salan ligands, bis-2-hydroxybenzamido derivatives, derivatives of the Trost ligand, porphyrin derivatives, derivatives of tetrabenzoporphyrin ligands, derivatives of corrole ligands, phthalocyaninate derivatives, and dibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives.
13. The method of claim 10, wherein the tetradentate ligand is selected from the group consisting of:
Figure imgf000170_0001
where: R2a and R2a', are independently a
Figure imgf000171_0001
(Z)m group, hydrogen, -OR, -NR2, -SR, -CN, -NO2, -SO2R, -SOR, -SO2NR2; -CNO, -NRSO2R, -NCO, -N3, -SiR3; or an optionally substituted radical selected from the group consisting of C1-20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur,
Rla, Rla, R3a, and R3a are independently a
Figure imgf000171_0002
(Z)m group, hydrogen, or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where any of [R2a and R3a'], [R2a and R3a], [Rla and R2a], and [Rla' and R2a'] may optionally be taken together with intervening atoms to form one or more rings which may in turn be substituted with one or more Rd groups;
Rd at each occurrence is independently a (Z)m group, hydrogen, halogen, -OR,
Figure imgf000171_0003
-NR2, -SR, -CN, -NO2, -SO2R, -SOR, -SO2NR2; -CNO, -NRSO2R, -NCO, -N3, -SiR3; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; where two or more Rd groups may be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms,
R , 4b is selected from the group consisting of:
Figure imgf000172_0001
d)
Figure imgf000172_0002
where
Rc at each occurrence is independently a
Figure imgf000172_0003
(Z)m group, hydrogen, halogen,
-OR, -NR2, -SR, -CN, -NO2, -SO2R, -SOR, -SO2NR2; -CNO, -NRSO2R, -NCO, -N3, -SiR3; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; where two or more Rc groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more optionally substituted rings; when two Rc groups are attached to the same carbon atom, they may optionally be taken together along with the carbon atom to which they are attached to form an optionally substituted moiety selected from the group consisting of: a 3- to 8-membered spirocyclic ring, a carbonyl, an oxime, a hydrazone, and an imine;
R at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; C1-6 aliphatic; C1-6 heteroaliphatic; carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an oxygen protecting group; and a nitrogen protecting group, where two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring,
X is a nucleophile capable of ring opening an epoxide; Y is a divalent linker selected from the group consisting of: -NR-, -N(R)C(O)-, -C(O)NR-, -O-, -C(O)-, -OC(O)-, -C(O)O-, -S-, -SO-, -SO2-, -SiR2-, -C(=S)-, -C(=NR)-, or -N=N-; a polyether; a C3 to C8 substituted or unsubstituted carbocycle; and a Ci to C8 substituted or unsubstituted heterocycle; m ' is O or an integer from 1 to 6, inclusive; m ' is O or an integer from 1 to 4, inclusive; q is O or an integer from 1 to 4, inclusive; and x is O, 1, or 2.
14. The method of claim 13, wherein
Figure imgf000174_0001
comprises:
Figure imgf000174_0002
15. The method of claim 14, wherein
Figure imgf000174_0003
comprises:
Figure imgf000174_0004
16. The method of claim 15, wherein the polymerization catalyst comprises:
Figure imgf000175_0001
wherein:
R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a' are each independently a
Figure imgf000175_0002
(Z)m group, hydrogen, halogen, -OR, -NR2, -SR, -CN, -NO2, -SO2R, -SOR, -SO2NR2; -CNO, -NRSO2R, -NCO, -N3, -SiR3; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur , where [R1 and R4a], [R1' and R4a'] and any two or more adjacent R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a groups can optionally be taken together with intervening atoms to form one or more optionally substituted rings; n is O or an integer from 1 to 8, inclusive; and p is O or an integer from 1 to 4, inclusive, where at least substituent is a (Z)m group.
Figure imgf000176_0002
17. The method of claim 15, wherein the polymerization catalyst is selected from the group consisting of:
Figure imgf000176_0001
18. The method of claim 16, wherein the polymerization catalyst is selected from the group consisting of:
Figure imgf000177_0001
19. The method of claim 18, wherein each R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a'is independently selected from the group consisting of: -H, optionally substituted C1--20 aliphatic, optionally substituted phenyl, and optionally substituted 8- to 10-membered aryl.
20. The method of claim 18, wherein each R4a, R4a', R6a, and R6a' is -H.
21. The method of claim 18, wherein each R4a, R4a', R6a, and R6a' is -H and each R5a, R5a', R7a, and R7a is independently -H, or an optionally substituted C1--20 aliphatic.
22. The method of claim 16, wherein the polymerization catalyst is selected from the group consisting of
Figure imgf000178_0001
23. The method of claim 22, wherein each R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a'is independently selected from the group consisting of: -H, optionally substituted C1--20 aliphatic, optionally substituted phenyl, and optionally substituted 8- to 10-membered aryl.
24. The method of claim 22, wherein each R4a, R4a', R6a, and R6a' is -H.
25. The method of claim 22, wherein each R4a, R4a', R6a, and R6a' is -H and each R5a, R5a', R7a, and R7a is independently -H, or an optionally substituted C1--20 aliphatic.
26. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000179_0001
27. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000179_0002
Figure imgf000180_0001
8. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000180_0002
Figure imgf000181_0001
29. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000181_0002
Figure imgf000182_0001
and
30. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000182_0002
Figure imgf000183_0001
31. The method of any of claims 26 to 30, wherein one or more Z group is independently a neutral functional group selected from the group consisting of amines, phosphines, gaunidines, bis-guanidines, amidines, and nitrogen-containing heterocycles.
32. The method of any of claims 26 to 30, wherein one or more Z group is a cationic moiety independently selected from the group consisting of:
Figure imgf000184_0001
33. The method of any of claims 26 to 33, wherein each linker moiety
Figure imgf000184_0002
is independently selected from the group consisting of:
Figure imgf000185_0001
where s = 0-6 and t = 1 -4
Figure imgf000185_0002
34. The method of any of claims 26 to 33, wherein M is selected from the group consisting of cobalt, aluminum, and chromium.
35. The method of any of claims 26 to 33, wherein M is selected from the group consisting of cobalt and chromium.
36. The method of any of claims 26 to 33, wherein M is cobalt.
37. The method of any of claims 26 to 36, wherein X is selected from the group consisting of: chlorine, bromine, an optionally substituted C1-12 carboxylate, azide, an optionally substituted phenoxide, a sulfonate salt, and a combination of any two or more of these.
38. The method of any of claims 26 to 36, wherein X is selected from the group consisting of chloride, acetate, trifluoroacetate, azide, pentafluorobenzoate, and a nitrophenolate.
39. The method of claim 1, wherein the polymerization catalyst is selected from Table 1.
40. The method of claim 1, wherein the polymerization catalyst contains a total of 1 to 8 Z groups.
41. The method of claim 1, wherein the polymerization catalyst contains a total of 1 to 6 Z groups.
42. The method of claim 1, wherein the polymerization catalyst contains a total of 1 to 4 Z groups.
43. The method of claim 1, wherein the polymerization catalyst contains a total of 2 Z groups.
44. The method of claim 1, wherein the polymerization catalyst contains a total of 4 Z groups.
45. The method of claim 1, wherein at least one Z group is selected from the group consisting of:
Figure imgf000187_0001
46. The method of claim 1, wherein at least one Z group is
Figure imgf000187_0002
47. The method of claim 46, wherein R1 and R2 are optionally substituted C1--20 aliphatic.
48. The method of claim 46, wherein R1 and R2 are optionally substituted C1-10 aliphatic.
49. The method of claim 46, wherein R1 and R2 are taken together to form an optionally substituted ring optionally containing additional heteroatoms.
50. The method of claim 1, wherein at least one Z group is selected from the group consisting of:
Figure imgf000188_0001
Figure imgf000188_0003
Figure imgf000188_0002
Figure imgf000188_0004
Figure imgf000188_0005
Figure imgf000188_0006
51. The method of claim 1 , wherein at least one Z group is selected from the group
consisting of:
Figure imgf000188_0007
52. The method of claim 51, wherein R1 and R2 are -H or optionally substituted C1--20 aliphatic.
53. The method of claim 51, wherein R1 and R2 are -H or optionally substituted C1-10 aliphatic.
54. The method of claim 51, wherein R5 is -H or optionally substituted C1-10 aliphatic.
55. The method of claim 51, wherein two or more of R1, R2, and R5 are taken together to form an optionally substituted ring optionally containing additional heteroatoms.
56. The method of claim 1, wherein at least one Z group is selected from the group consisting of:
Figure imgf000189_0001
57. The method of claim 1, wherein at least one Z group is selected from the group
consisting of:
Figure imgf000189_0002
58. The method of claim 57, wherein R1, R1 , R1 , R2, R2 , and R3 and are independently H or optionally substituted C1--20 aliphatic.
59. The method of claim 57, wherein R1, R1', R1," R2, R2', and R3 are independently -H or optionally substituted C1--10 aliphatic.
60. The method of claim 57, wherein two or more of R1, R1 , R1 , R2, R2 , and R3 are taken together to form one or more optionally substituted rings optionally containing additional heteroatoms.
61. The method of claim 1, wherein at least one Z group is selected from the group consisting of:
Figure imgf000190_0001
62. The method of claim 1, wherein at least one Z group is .
Figure imgf000190_0002
63. The method of claim 62, wherein R1, R1 , R1 , R2, and R2 are independently -H or optionally substituted C1--20 aliphatic.
64. The method of claim 62, wherein R1, R1 , R1 , R2, and R2 are independently -H or optionally substituted C1-10 aliphatic.
65. The method of claim 62, wherein two or more of R1, R1 , R1 , R2, and R2 are taken together to form one or more optionally substituted rings optionally containing additional heteroatoms.
66. The method of claim 1, wherein at least one Z group is selected from the group
consisting or:
Figure imgf000191_0001
, and
67. The method of claim 1, wherein at least one Z group is selected from the group consisting of:
Figure imgf000191_0002
68. The method of claim 1, wherein the epoxide has the formula:
Figure imgf000191_0003
wherein:
Ra is hydrogen or an optionally substituted radical selected from the group consisting of C1-30 aliphatic; C1-30 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and
each of Rb , Rc , and Rd is independently hydrogen or an optionally substituted radical selected from the group consisting of C1-12 aliphatic; C1-12 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
wherein any of (Ra and Rc ), (Ro' and Rd ), and (Ra' and Rb ) can be taken together with intervening atoms to form one or more optionally substituted rings.
69. The method of claim 68, wherein a polymer formed has a formula selected from the group consisting of:
Figure imgf000193_0001
70. The method of claim 68, wherein Rb , Rc , and Rd are each hydrogen.
71. The method of claim 68, wherein Ra is optionally substituted C1-12 aliphatic.
72. The method of claim 1, wherein the epoxide is selected from the group consisting of: ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, 1,2 octene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin and mixtures of any two or more of these.
73. The method of claim 1, wherein the epoxide is ethylene oxide, propylene oxide, or cyclohexene oxide.
74. The method of claim 1, wherein the epoxide is propylene oxide.
75. The method of claim 1, wherein the CO2 pressure is between about 50 and 800 psi.
76. The method of claim 1, wherein the ratio of catalyst to epoxide is between about 1 :1000 and about 1 :100,000.
77. The method of claim 1, further comprising the steps of letting the polymerization proceed until a desired polymer molecular weight has been achieved, quenching the polymerization reaction and isolating the polymer.
78. A polymerization catalyst having the structure:
Figure imgf000194_0001
wherein:
M is a metal atom;
Figure imgf000194_0003
comprises a multidentate ligand; and
Figure imgf000194_0004
(Z)m represents one or more activating moiety tethered to the multidentate ligand, where
Figure imgf000194_0005
represents a linker moiety; m represents the number of Z groups present on a linker moiety and is an integer between 1 and 4 inclusive; and each (Z) is an activating functional group independently selected from the group consisting of:
Figure imgf000194_0002
Figure imgf000195_0003
R
Figure imgf000195_0001
Figure imgf000195_0002
wherein: each occurrence of R1, R2 and R3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6- membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8- membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly eye lie saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein two or more R1, R2 and R3 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms;
R4 is hydrogen, hydroxyl, optionally substituted C1--20 aliphatic;
each occurrence of R5 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1 -3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly eye lie saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein an R5 group can be taken with an R1 or R2 group to form one or more optionally substituted rings;
each occurrence of R7 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C1--20 acyl; C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where an R7 group can be taken with an R5 group to form one or more optionally substituted rings optionally containing one or more heteroatoms;
each occurrence of R7 , is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C1--20 acyl; C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and where two R7 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, and an R7 group can be taken with an R1 or R2 group to form one or more optionally substituted rings optionally containing one or more heteroatoms; each occurrence of R8, R9, and R10 is independently hydrogen or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1 -3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly eye lie saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10- membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more R8, R9 and R10 groups can be taken together with intervening atoms to form one or more optionally substituted rings;
each occurrence of R11 is independently selected from the group consisting of: halogen, -NO2, -CN, -SRy, -S(O)Ry, -S(O)2Ry, -NRyC(O)Ry, -OC(O)Ry, -CO2Ry, -NCO, -N3, -OR7, -OC(O)N(Ry)2, -N(Ry)2, -NRyC(0)Ry, -NRyC(0)0Ry; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8- membered saturated or partially unsaturated monocyclic carbocycle, a 7- 14 carbon saturated, partially unsaturated or aromatic poly eye lie carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where each occurrence of Ry is independently selected from the group consisting of hydrogen an optionally substituted C1-6 aliphatic group, and an optionally substituted aryl group, where two or more adjacent R11 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;
X is an anion;
ring A is an optionally substituted 5- to 10-membered heteroaryl group having 0 to 4 additional heteroatoms independently selected from nitrogen, oxygen, or sulfur;
with the provisos that:
when Z is
Figure imgf000199_0001
, ring A is not an imidazole, an oxazole, or a thiazole; and
where -CH2-
Figure imgf000199_0005
Figure imgf000199_0002
79. The polymerization catalyst of claim 78, wherein
Figure imgf000199_0003
comprises:
Figure imgf000199_0004
80. The polymerization catalyst of claim 79, wherein
Figure imgf000200_0001
comprises:
Figure imgf000200_0002
81. The polymerization catalyst of claim 80 having a structure selected from the group consisting of:
Figure imgf000200_0003
wherein:
R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R 7a' are each independently a
Figure imgf000200_0004
(Z)m group, hydrogen, halogen, -OR, -NR2, -SR, -CN, -NO2, -SO2R, -SOR, -SO2NR2; -CNO, -NRSO2R, -NCO, -N3, -SiR3; or an optionally substituted radical selected from the group consisting of C1--20 aliphatic; C1--20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic poly cyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered poly cyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where [R1 and R4a], [R1' and R4a'] and any two or more adjacent R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a groups can optionally be taken together with intervening atoms to form one or more optionally substituted rings; n is 0 or an integer from 1 to 8, inclusive; and p is 0 or an integer from 1 to 4, inclusive, where at least substituent is a
Figure imgf000201_0002
(Z)m group.
82. The polymerization catalyst of claim 80 having a structure selected from the group consisting of:
Figure imgf000201_0001
83. The polymerization catalyst of claim 82, having a structure selected from the group consisting of:
Figure imgf000202_0001
84. The polymerization catalyst of claim 83, wherein each R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a is independently selected from the group consisting of: -H, optionally substituted C1--20 aliphatic, optionally substituted phenyl, and optionally substituted 8- to 10-membered aryl.
85. The polymerization catalyst of claim 83, wherein each R4a, R4a, R6a, and R6a is -H.
86. The polymerization catalyst of claim 83, wherein each R 4a, R 4a', R 6a, and R 6a' is -H and each R5a, R5a, R7a, and R7a is independently -H, or an optionally substituted C1-: 20 aliphatic.
87. The polymerization catalyst of claim 83, wherein the polymerization catalyst is selected from the group consisting of
Figure imgf000203_0001
88. The polymerization catalyst of claim 87, wherein each R4a, R4a', R5a, R5a', R6a, R6a', R7a, and R7a is independently selected from the group consisting of: -H, optionally substituted C1--20 aliphatic, optionally substituted phenyl, and optionally substituted 8- to 10-membered aryl.
89. The polymerization catalyst of claim 87, wherein each R4a, R4a', R6a, and R6a' is -H.
90. The polymerization catalyst of claim 87, wherein each R 4a , R 4a' , R 6a , and R 6a' is -H and each R5a, R5a, R7a, and R7a is independently -H, or an optionally substituted C1-: 20 aliphatic.
91. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000204_0001
92. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000204_0002
Figure imgf000205_0001
93. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000205_0002
Figure imgf000206_0001
94. The polymerization catalyst of claim 81, wherein at least one salicylaldehy de-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000206_0002
Figure imgf000207_0001
Figure imgf000207_0002
Figure imgf000207_0003
and
95. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:
Figure imgf000208_0001
207
Figure imgf000209_0001
96. The polymerization catalyst of any of claims 91 to 95, wherein one or more Z group is independently a neutral functional group selected from the group consisting of amines, phosphines, gaunidines, bis-guanidines, amidines, and nitrogen-containing heterocycles.
97. The polymerization catalyst of any of claims 91 to 95, wherein one or more Z group is a cationic moiety independently selected from the group consisting of:
Figure imgf000210_0001
98. The polymerization catalyst of any of claims 91 to 95, wherein each linker moiety
Figure imgf000210_0002
" is independently selected from the group consisting of:
Figure imgf000211_0001
Figure imgf000211_0002
Figure imgf000211_0003
Figure imgf000211_0005
Figure imgf000211_0004
Figure imgf000211_0006
where s = 0-6 and t = 1 -4
Figure imgf000211_0007
99. The polymerization catalyst of any of claims 91 to 98, wherein M is selected from the group consisting of cobalt, aluminum, and chromium.
100. The polymerization catalyst of any of claims 91 to 98, wherein M is selected from the group consisting of cobalt and chromium.
101. The polymerization catalyst of any of claims 91 to 98, wherein M is cobalt.
102. The polymerization catalyst of any of claims 91 to 101, wherein X is selected from the group consisting of: chlorine, bromine, an optionally substituted C1-12 carboxylate, azide, an optionally substituted phenoxide, a sulfonate salt, and a combination of any two or more of these.
103. The polymerization catalyst of claim 83, wherein the catalyst metal complex has a structure selected from those in Table 1.
104. The polymerization catalyst of claim 79, wherein the catalyst has a structure selected from those in Table 1.
105. The polymerization catalyst of claim 79, wherein the catalyst has a structure selected from those in Table 2.
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