WO2020109217A2 - Metal organic compounds - Google Patents

Metal organic compounds Download PDF

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Publication number
WO2020109217A2
WO2020109217A2 PCT/EP2019/082393 EP2019082393W WO2020109217A2 WO 2020109217 A2 WO2020109217 A2 WO 2020109217A2 EP 2019082393 W EP2019082393 W EP 2019082393W WO 2020109217 A2 WO2020109217 A2 WO 2020109217A2
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Prior art keywords
optionally substituted
alkyl
cycloalkyl
aryl
halogen
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PCT/EP2019/082393
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French (fr)
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WO2020109217A3 (en
Inventor
Adam M. Johns
Richard L. Pederson
Doina Gabriela ENE
Ralf Karch
Angelino Doppiu
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Umicore Ag & Co. Kg
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Publication of WO2020109217A2 publication Critical patent/WO2020109217A2/en
Publication of WO2020109217A3 publication Critical patent/WO2020109217A3/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/825—Osmium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated

Definitions

  • This invention relates generally to olefin metathesis catalysts comprising cyclic alkyl amino carbenes, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins.
  • the invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals and pharmaceuticals.
  • ruthenium metathesis catalysts have enabled the development of several research platforms including: ring opening metathesis polymerization (ROMP), ring opening cross metathesis (ROCM), cross metathesis (CM), ring closing metathesis (RCM).
  • ROMP ring opening metathesis polymerization
  • CCM cross metathesis
  • RCM ring closing metathesis
  • N-Heterocyclic Carbene (NHC) ligands have played an essential role in the development of ruthenium metathesis catalysts.
  • Metathesis catalysts, based on ruthenium, are known and have been studied.
  • M is Ru or Os; typically, M is Ru;
  • L 2 and L 3 are independently neutral ligands
  • n 0, 1 or 2; generally, m is 0 or 1; typically, m is 0;
  • n is 0 or 1; generally, n is 0;
  • k is 0 or 1; generally, k is 1;
  • X 1 and X 2 are independently anionic ligands; generally, X 1 and X 2 are independently halogen, trifluoroacetate, per-fluorophenols, -NCO, -CN, -NCS, -N 3 ; or X 1 together with X 2 can form a nitrate; typically, X 1 and X 2 are independently halogen, or -NCO;
  • R 1 and R 2 are independently selected from hydrogen, optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl; or any two or more of X 1 , X 2 , L 2 , L 3 , R 1 , and R 2 are taken together to form one or more cyclic groups;
  • X is -CR la R 2a -;
  • a is 1 or 2;
  • R la is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3 -8 cycloalkyl, halogen, optionally substituted C 5 -C 24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C 1 -C 20 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , N0 2 , -CF 3 , -S(0) x R 25 , -P(0)(OH) 2 , - OP(0)(OH)2, -SR 27 , or together with R 2a forms an optionally substituted spiro monocyclic or spiro polycyclic C 3-10 cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R 3 or together with R 4 forms an optionally substituted polycyclic ring; R 2a is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3
  • Y is -CR lb R 2b -;
  • b 0, 1 or 2;
  • R lb is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, halogen, optionally substituted C 5 -C 24 aryl, optionally substituted C 6 -C 24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , N0 2 , -CF 3 , -S(0) x R 25 , -P(0)(0H) 2 , - 0P(0)(0H)2, -SR 27 , or together with R 2b forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
  • R 2b is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, halogen, optionally substituted C 5 -C 24 aryl, optionally substituted C 6 -C 24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , N0 2 , -CF 3 , -S(0) x R 25 , -P(0)(0H) 2 , - 0P(0)(0H) 2 , -SR 27 , or together with R lb forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
  • R 3 is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 2 , -CF 3 , -S(0) x R 25 , -P(0)(0f[)2, -0P(0)(0H)2, -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R la or together with R 2a can form an optionally substituted polycyclic ring, or together with R 3a can form an optionally substituted spiro monocyclic or spiro polycyclic C 3-10 cycloalkyl;
  • R 3a is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 2 , - CFs, -S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R la or together with R 2a can form an optionally substituted polycyclic ring, or together with R 3 can form an optionally substituted spiro monocyclic or spiro polycyclic C 3-10 cycloalkyl; R 4 is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -
  • R 4a is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, - CF 3 , - S(0) x R 25 , -P(0)(0H) 2 , -OP(0)(OH) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R la or together with R 2a can form an optionally substituted polycyclic ring, or together with R 4 can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl;
  • R 5 is H, optionally substituted Ci-24 alkyl, halogen- C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0)xR 25 , -P(0)(0F1) 2 , -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkcnyl, or together with R 6 can form an optionally substituted polycyclic ring;
  • R 6 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0)xR 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R 5 or together with R 7 can form an optionally substituted polycyclic ring;
  • R 7 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R 6 or together with R 8 can form an optionally substituted polycyclic ring;
  • R 8 is H, optionally substituted Ci-24 alkyl, halogen- C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R 7 or together with R 9 can form an optionally substituted polycyclic ring;
  • R 9 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0) x R 25 , -P(0)(0H)2, -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle
  • R 21 is OH, OR 26 , NR 23 R 24 , optionally substituted C1-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 22 is H, optionally substituted C i-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 23 is H, optionally substituted C i-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 24 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 25 is H, optionally substituted Ci-24 alkyl, OR 22 , - NR 23 R 24 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 26 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 27 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
  • x 1 or 2; and with the provisos
  • the "Y-Y" bond can be saturated or unsaturated
  • R 3a and R 4a are both nil; f. when b is 2, and the "Y-Y" bond is unsaturated, then R 2b is nil.
  • the invention provides a method of synthesizing the olefin metathesis catalysts of the invention.
  • the invention provides a method of using the olefin metathesis catalysts of the invention in metathesis reactions.
  • the olefin metathesis catalysts of the invention are of particular benefit for use in metathesis reactions, such as ring opening metathesis polymerization reactions, ring-opening cross metathesis reactions, cross metathesis reactions, ring-closing metathesis reactions, self-metathesis reactions, as well as combinations of such metathesis reactions.
  • the olefin metathesis catalysts of the invention are also key intermediates in the synthesis of a variety of ruthenium olefin metathesis catalysts.
  • alkyl refers to a linear, branched, saturated hydrocarbon group typically containing 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms: such as methyl (Me), ethyl (Et), n-propyl (Pr or n-Pr), isopropyl (i-Pr), n-butyl (Bu or n-Bu), isobutyl (i-Bu), t-butyl (t-Bu), octyl (Oct), decyl, and the like.
  • cycloalkyl refers to a cyclic alkyl group, can be monocyclic, bicyclic or polycyclic, typically having 3 to 10, preferably 5 to 7, carbon atoms, generally, cycloalkyl groups are cyclopentyl (Cp), cyclohexyl (Cy), adamantly.
  • substituted alkyl refers to alkyl substituted with one or more substituent groups
  • heteroatom-containing alkyl and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom
  • alkylene refers to a difunctional linear, branched alkyl group, where "alkyl” is as defined above.
  • alkenyl refers to a linear, branched hydrocarbon group of 2 to 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, iso- propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, and the like.
  • Preferred alkenyl groups herein contain 2 to 12 carbon atoms, more preferred alkenyl groups herein contain 2 to 6 carbon atoms.
  • substituted alkenyl refers to alkenyl substituted with one or more substituent groups
  • heteroatom-containing alkenyl and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom.
  • cycloalkenyl refers to a cyclic alkenyl group, preferably having 3 to 8 carbon atoms.
  • alkenylene refers to a difunctional linear, branched, where "alkenyl” is as defined above.
  • alkynyl refers to a linear or branched hydrocarbon group of 2 to 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like.
  • Preferred alkynyl groups herein contain 2 to 12 carbon atoms, more preferred alkynyl groups herein contain 2 to 6 carbon atoms.
  • substituted alkynyl refers to alkynyl substituted with one or more substituent groups
  • heteroatom-containing alkynyl and heteroalkynyl refer to alkynyl in which at least one carbon atom is replaced with a heteroatom
  • alkynylene refers to a difunctional alkynyl group, where "alkynyl” is as defined above.
  • alkoxy refers to an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy” group may be represented as -O-alkyl where "alkyl” is as defined above.
  • alkenyloxy refer to an alkenyl group bound through a single, terminal ether linkage
  • alkynyloxy refers to an alkynyl group bound through a single, terminal ether linkage.
  • aryl refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety).
  • Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 6 to 10 carbon atoms.
  • Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl (Ph), naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, phenanthryl and the like.
  • Substituted aryl refers to an aryl moiety substituted with one or more substituent groups
  • heteroatom containing aryl and “heteroaryl” refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail herein.
  • aryloxy refers to an aryl group bound through a single, terminal ether linkage, wherein "aryl” is as defined above.
  • An "aryloxy” group may be represented as -O-aryl where aryl is as defined above.
  • Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 6 to 10 carbon atoms.
  • aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p- halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy- phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.
  • alkaryl refers to an aryl group with an alkyl substituent
  • aralkyl refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above.
  • Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms.
  • Alkaryl groups include, without limitation, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7- dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta- 1,4-diene, and the like.
  • aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl- butyl, 5-phenyl-pentyl, 4-phenyl cyclohexyl, 4-benzylcyclohexyl, 4-phenyl cyclohexylmethyl, 4- benzylcyclohexylmethyl, and the like.
  • alkaryloxy and “aralkyloxy” refer to substituents of the formula -OR wherein R is alkaryl or aralkyl, respectively, as defined herein.
  • acyl refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, - (CO)-aralkyl, -(CO)-alkaryl, -(CO)-alkenyl, or -(CO)-alkynyl
  • acyloxy refers to substituents having the formula -0(CO)-alkyl, -0(CO)-aryl, -0(CO)-aralkyl, -0(CO)-alkaryl, - 0(CO)-alkenyl, or -(CO)-alkynyl wherein "alkyl,” “aryl”, “aralkyl”, “alkaryl”, “alkenyl", and “alkynyl” are as defined above.
  • acetoxy group (-0(CO)CH 3 , often abbreviated as -OAc) is a common example of an acyloxy group.
  • cyclic and ring refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic.
  • alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic or polycyclic.
  • polycyclic ring refers to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that have at least two closed rings tethered, fused, linked via a single bond or bridged.
  • Polycyclic rings include without limitation naphthyl, biphenyl, phenanthryl and the like.
  • spiro compound refers to a chemical compound, that presents a twisted structure of two or more rings (a ring system), in which 2 or 3 rings are linked together by one common atom,
  • halo and “halogen” and “halide” are used in the conventional sense to refer to a fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) substituent.
  • Hydrocarbyl refers to univalent hydrocarbyl moieties containing 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like.
  • Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups.
  • Hydrocarbylene refers to divalent hydrocarbyl moieties containing 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, formed by removal of two hydrogens from a hydrocarbon.
  • Substituted hydrocarbylene refers to hydrocarbylene substituted with one or more substituent groups.
  • heteroatom-containing refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur.
  • heteroatom-containing hydrocarbylene and heterohydrocarbylene refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom.
  • heteroalkyl refers to an alkyl substituent that is heteroatom-containing
  • heterocyclic refers to a cyclic substituent that is heteroatom-containing
  • heteroaryl and “heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like.
  • a “heterocyclic” group or compound may or may not be aromatic, and further that
  • heterocycles may be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl.”
  • heteroalkyl groups include without limitation alkoxyaryl,
  • heteroaryl substituents include without limitation pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc.
  • heteroatom-containing alicyclic groups include without limitation pyrrolidino, morpholino, piperazino, piperidino, etc.
  • the aforementioned substituent groups may, if a particular group permits, be further substituted with one or more additional substituent groups or with one or more hydrocarbyl moieties such as those specifically enumerated above.
  • the above mentioned hydrocarbyl moieties may be further substituted with one or more substituent groups or additional hydrocarbyl moieties such as those specifically mentioned above.
  • the above-mentioned hydrocarbylene moieties may be further substituted with one or more substituent groups or additional hydrocarbyl moieties as noted above.
  • substituted as in “substituted hydrocarbyl”, “substituted alkyl”, “substituted aryl”, and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents.
  • substituents include, without limitation groups such as halo, hydroxyl, sulfhydryl, C 1 -C 24 alkoxy, C 2 -C2 4 alkenyloxy, C2-C 24 alkynyloxy, C 5 -C2 4 aryloxy, C6-C24 aralkyloxy, C6-C24 alkaryloxy, acyl (including C 2 -C 24 alkylcarbonyl (-CO-alkyl) and C 6 -C 24 arylcarbonyl (-CO-aryl)), acyloxy (-0- acyl, including C 2 -C 24 alkylcarbonyloxy (-O-CO-alkyl) and C 6 -C 24 arylcarbonyloxy (-O-CO- aryl)), C 2 -C 24 alkoxycarbonyl (-(CO)-O-alkyl), C 6 -C 24 aryloxycarbonyl (-(CO)-aryl), halocarbon
  • “functionalized” as in “functionalized hydrocarbyl”, “functionalized alkyl”, “functionalized olefin”, “functionalized cyclic olefin”, and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one H atom bound to a carbon (or other) atom is replaced with one or more functional group(s) such as those described hereinabove.
  • the term “functional group” is meant to include any functional species that is suitable for the uses described herein. In some cases, the terms “substituent” and “functional group” are used interchangeably.
  • hydroxyl as used herein, represents a group of formula "-OH”.
  • carbonyl as used herein, represents a group of formula "-C(O)- ".
  • ketone represents an organic compound having a carbonyl group linked to a carbon atom such as -C(0)R x , wherein R x can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • esters represents an organic compound having a carbonyl group linked to a carbon atom such as -C(0)OR x wherein R x can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • amine as used herein, represents a group of formula "-NR x R y ", wherein R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • amide as used herein, represents a group of formula "-C(0)NR x R y ", wherein R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • sulfonamide represents a group of formula "-S(0) 2 NR x R y " wherein R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • sulfoxide as used herein, represents a group of formula "-S(O)- ".
  • phosphonic acid as used herein, represents a group of formula "-P(0)(OH) 2 ".
  • phosphoric acid as used herein, represents a group of formula 0P(0)(0H) 2 ".
  • N represents a nitrogen atom
  • Functional groups may be protected in cases where the functional group interferes with the metal carbene olefin metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 5th Ed. (New York: Wiley, 2014). Examples of protecting groups include acetals, cyclic acetals, boronate esters (boronates), cyclic boronate esters (cyclic boronates), carbonates, or the like. Examples of protecting groups include cyclic acetals or cyclic boronate esters.
  • the invention provides olefin metathesis catalysts, represented by the structure of Formula (I), as described herein.
  • the invention provides a metal carbene olefin metathesis catalyst, represented by the structure of Formula (II), as represented below:
  • Table (1) illustrates possible moieties which form general Formula (I) and general Formula (II).
  • substructures of the Moiety (A) are exemplified in Table (1).
  • substructures of Moiety (B) are exemplified in Table (1).
  • substructures of Moiety (C) are exemplified in Table (1). Any combination of a Moiety (A), Moiety (B) and Moiety (C) can form a ruthenium carbene olefin metathesis catalyst of the invention, according to Formula (I) and Formula (II).
  • M is Ru
  • X 1 is an anionic ligand; generally, X 1 is halogen, trifluoroacetate, per-fluorophenols, - NCO, -CN, -NCS, -N 3, ; or together with X 2 can form a nitrate; typically; X 1 is halogen, or - NCO; specifically, in the present case X 1 is Cl;
  • X 2 is an anionic ligand; generally, X 2 is halogen, trifluoroacetate, per-fluorophenols, - NCO, -CN, -NCS, -N 3 ; or together with X 1 can form a nitrate; typically, X 2 is halogen, or -NCO; specifically, in the present case X 2 is Cl; or X 1 and X 2 together with the ruthenium can form
  • R 1 is hydrogen, optionally substituted hydrocarbyl, or optionally substituted heteroatom- containing hydrocarbyl; generally, R 1 is H; or together with R 2 can form a substituted indenylidene;
  • R 2 is hydrogen, optionally substituted hydrocarbyl, optionally substituted heteroatom- containing hydrocarbyl; generally, R 2 is optionally substituted C 2-24 alkenyl or optionally substituted phenyl or together with R 1 can form a substituted indenylidene;
  • X is -CR la R 2a -;
  • a is 1 or 2; generally, a is 2;
  • R la is H, optionally substituted Ci-24 alkyl, optionally substituted C 3-8 cycloalkyl, halogen, optionally substituted C 5 -C 24 aryl, optionally substituted C 6 -C 24 aralkyl, optionally substituted C 1 -C 20 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , N0 2 , -CF 3 , -S(0) x R 25 , -P(0)(OH) 2 , - OP(0)(OH) 2 , -SR 27 , or together with R 2a forms an optionally substituted spiro monocyclic or spiro polycyclic C 3-10 cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R 3 or together with R 4 forms an optionally substituted polycyclic ring;
  • R 2a is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, halogen, optionally substituted C 5 -C 24 aryl, optionally substituted C 6 -C 24 aralkyl, optionally substituted C 1 -C 20 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF 3 , -S(0) x R 25 , -P(0)(0H) 2 , - 0P(0)(0H) 2 , -SR 27 , or together with R la forms a spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R 3 or together with R 4 forms an optionally substituted polycyclic ring;
  • Y is -CR lb R 2b -;
  • b is 0, 1 or 2; generally, b is 0 or 1; typically, b is 0;
  • R lb is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3 -8 cycloalkyl, halogen, optionally substituted C 5 -C 24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C 1 -C 20 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , N0 2 , -CF 3 , -S(0) x R 25 , - P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 27 , or together with R 2b forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
  • R 2b is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, halogen, optionally substituted C 5 -C 24 aryl, optionally substituted C 6 -C 24 aralkyl, optionally substituted C 1 -C 20 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF 3 , -S(0) x R 25 , - P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 27 , or together with R lb forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
  • R 3 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0)xR 25 , -P(0)(0F1) 2 , -OP(0)(OH) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R 3a can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or together with R la or together with R 2a can form an optionally substituted polycyclic ring;
  • R 3a is FI, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 2 , -CF 3 , -S(0) x R 25 , -P(0)(0F1) 2 , -0P(0)(0H)2, -SR 27 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R 3 can form an optionally substituted spiro monocyclic or spiro polycyclic C 3-10 cycloalkyl or together with R la or together with R 2a can form an optionally substituted polycyclic ring;
  • R 4 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0)xR 25 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R 4a can form an optionally substituted spiro monocyclic or spiro polycyclic C 3-10 cycloalkyl or together with R la or together with R 2a can form an optionally substituted polycyclic ring;
  • R 4a is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 2 , -CF 3 , -S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl, or together with R 4 can form an optionally substituted spiro monocyclic or spiro polycyclic C 3-10 cycloalkyl or together with R la or together with R 2a can form an optionally substituted polycyclic ring;
  • W is O, NR 20 or S;
  • R I0 is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 2 , -CF 3 , -S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl or together with R n can form a polycyclic ring;
  • R 11 is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 2 , -CF 3 , -S(0) x R 25 , -P(0)(0H) 2 , -OP(0)(OH) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 5 -2 4 aryl, optionally substituted C 3-8 cycloalkenyl or together with R 10 or together with R 12 can form a polycyclic ring;
  • R 12 is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 3 ⁇ 4 -CF 3 , -S(0) X R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , -NHC(0)CF 3 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl or together with R 11 or together with R 13 can form a polycyclic ring;
  • R 13 is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 2 , -CF 3 , -S(0) X R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 5-24 aryl, optionally substituted C 3-8 cycloalkenyl or together with R 12 can form a polycyclic ring;
  • R 14 is H, optionally substituted Ci- 24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 2 , -CF 3 , -S(0) x R 25 , -P(0)(0H)2, -0P(0)(0H)2, -SR 27 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 5-24 aryl or optionally substituted C 3-8 cycloalkenyl;
  • R 15 is H, optionally substituted Ci- 24 alkyl, -C(R 28 )(R 29 )COOR 30 , -C(R 28 )(R 29 )C(0)H, - C(R 28 )(R 29 )C(0)R 31 , -C(R 28 )(R 29 )CR 32 (OR 33 )(OR 34 ), -C(R 28 )(R 29 )C(0)NR 35 R 36
  • R 16 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0)xR 25 , -P(0)(0H)2, -0P(0)(0H) 2 , -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 17 can form an optionally substituted polycyclic ring;
  • R 17 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0)xR 25 , -P(0)(0H) 2 , -0P(0)(0H)2, -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 16 or together with R 18 can form an optionally substituted polycyclic ring;
  • R 18 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 ,
  • S(0) x R 25 , -P(0)(0F1)2, -0P(0)(0H)2, -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted Cs-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 17 or together with R 19 can form an optionally substituted polycyclic ring;
  • R 18a is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0)xR 25 , -P(0)(0H)2, -0P(0)(0H)2, -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 16 can form an optionally substituted polycyclic ring;
  • R 19 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, -S(0)xR 25 , -P(0)(0H) 2 , -0P(0)(0H)2, -SR 27 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted Cs-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 18 can form an optionally substituted polycyclic ring.
  • R 20 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R 15 can form an optionally substituted heterocyclic ring;
  • R 21 is OH, OR 26 , NR 23 R 24 , optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5 -24 aryl or optionally substituted C 3-8 cycloalkenyl;
  • R 22 is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 23 is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 24 is H, optionally substituted Ci- 24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl or optionally substituted C 3-8 cycloalkenyl;
  • x is 1 or 2;
  • R 25 is H, optionally substituted Ci- 24 alkyl, OR 22 , - NR 23 R 24 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 5-24 aryl or optionally substituted C 3-8 cycloalkenyl;
  • R 26 is optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl or optionally substituted C 3-8 cycloalkenyl;
  • R 27 is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl or optionally substituted C 3-8 cycloalkenyl;
  • R 28 is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl or optionally substituted C 3 -8 cycloalkenyl;
  • R 29 is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R 19 can form an optionally substituted heterocyclic ring;
  • R 30 is H, optionally substituted Ci- 24 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 5-24 aryl or optionally substituted C 3-8 cycloalkenyl;
  • R 31 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 32 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 33 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 34 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 35 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 36 is II, optionally substituted Ci-24 alkyl, - OR 22 , optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • X 3 is O or S; typically, X 3 is S;
  • X 4 is O or S; typically, X 4 is S;
  • X 5 is CN or NO2; typically, X 5 is CN;
  • X 6 is CN or NO2; typically, X 6 is CN; and
  • the "Y-Y" bond can be saturated or unsaturated
  • the invention provides olefin metathesis catalysts, wherein the nomenclature of the olefin metathesis catalysts is determined by the combination of Moieties (A), (B), and (C) according to Table (1).
  • olefin metathesis catalyst represented by the structure shown below is of general Formula (I) and is composed of Moiety (A13), Moiety (B2) and Moiety (C3), therefore it is assigned Formula (IA13B2C3):
  • the olefin metathesis catalyst represented by the structure shown below is of general Formula (II) and is composed of two Moieties (A9), Moiety (B4) and Moiety (C2), therefore it is assigned Formula (IIA9B4C2A9):
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IAB4C3),
  • X 1 is halogen
  • X 2 is halogen
  • X is -CR la R 2a -;
  • R la is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl or optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, - S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , or -SR 27 ;
  • R 2a is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, - S(0)xR 25 , -P(0)(0H) 2 , -0P(0)(0H 2 , or -SR 27 ;
  • a is 1 or 2;
  • Y is -CR lb R 2b - ;
  • R lb is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C ⁇ -Ce heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF 3 , - S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , or -SR 27 ;
  • R 2b is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3,— S(0)xR 25 , -P(0)(0H)2, -0P(0)(0H) 2 , or -SR 27 ;
  • b 0, 1 or 2;
  • R 3 is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Ci-Ce heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, - S(0)xR 25 , -P(0)(0H) , -OP(0)(OH) 2 , or -SR 27;
  • R 3a is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, - S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , or -SR 27 ;
  • R 4 is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C 1 -C 6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2,
  • R 4a is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Ci-Ce heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, - S(0) x R 25 , -P(0)(0H> 2 , -0P(0)(0H) 2 , -SR 27 , or together with R 4 forms an optionally substituted spiro cyclohexyl or adamantyl;
  • R 5 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 6 can form an optionally substituted polycyclic ring;
  • R 6 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 5 or together with R 7 can form an optionally substituted polycyclic ring;
  • R 7 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 6 or together with R 8 can form an optionally substituted polycyclic ring;
  • R 8 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 7 or together with R 9 can form an optionally substituted polycyclic ring;
  • R 9 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 8 can form a polycyclic ring;
  • W is O, S, or NR 20 ;
  • R 10 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 11 can form a polycyclic ring;
  • R 11 is FI, optionally substituted Ci- 6 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO 2 , -CF 3 , -S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H)2, -SR 27 , optionally substituted cyclohexyl, optionally substituted cyclopentyl, optionally substituted phenyl, optionally substituted benzyl or together with R 10 or together with R 12 can form a polycyclic ring;
  • R 12 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 11 or together with R 13 can form a polycyclic ring;
  • R 13 is H, optionally substituted Ci- 6 alkyl, optionally substituted phenyl, or together with R 12 can form a polycyclic ring;
  • R 14 is H, or optionally substituted Ci- 6 alkyl;
  • R 15 is optionally substituted Ci- 6 alkyl, -C(R 28 )(R 29 )COOR 30 , -C(R 28 )(R 29 )C(0)H, - C(R 28 )(R 29 )C(0)R 31 , -C(R 28 )(R 29 )CR 32 (OR 33 )(OR 34 ), -C(R 28 )(R 29 )C(0)NR 35 R 36 , - C(R 28 )(R 29 )C(0)NR 35 0R 34 , C(R 28 )(R 29 )C(0)NR 35 0R 34 , - C(0)R 21 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted phenyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, or together with R 20 can form an optionally substituted heterocyclic ring;
  • R 20 is H, optionally substituted Ci-6 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted phenyl, or together with R 15 can form an optionally substituted heterocyclic ring;
  • R 21 is OH, OR 26 , NR 23 R 24 , or optionally substituted Ci- 6 alkyl;
  • R 22 is H, or optionally substituted Ci- 6 alkyl
  • R 23 is H, or optionally substituted Ci- 6 alkyl
  • R 24 is H, or optionally substituted Ci- 6 alkyl
  • R 25 is H, or optionally substituted Ci- 6 alkyl, OR 22 , - NR 23 R 24 ;
  • R 26 is optionally substituted Ci- 6 alkyl
  • R 27 is H, or optionally substituted Ci- 6 alkyl
  • R 28 is H, or optionally substituted Ci- 6 alkyl
  • R 29 is H, or optionally substituted Ci- 6 alkyl
  • R 30 is H, or optionally substituted Ci 6 alkyl
  • R 31 is H, or optionally substituted Ci- 6 alkyl
  • R 32 is H, or optionally substituted Ci- 6 alkyl
  • R 33 is H, or optionally substituted Ci- 6 alkyl
  • R 34 is H, or optionally substituted Ci- 6 alkyl
  • R 35 is H, or optionally substituted Ci- 6 alkyl
  • R 36 is H, or optionally substituted C 1-6 alkyl
  • x is 1 or 2.
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IAB4C3):
  • X is -CR la R 2a -;
  • R la is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR 23 R 24 , F, Cl, Br, or I;
  • R 2a is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR 23 R 24 , F, Cl, Br, or I;
  • a 2;
  • Y is -CR lb R 2b -;
  • R lb is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR 23 R 24 , F, Cl, Br, or I;
  • R 2b is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, - R 23 R 24 , F, Cl, Br, or I;
  • b 0, 1 or 2;
  • W is O
  • R 3 is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 3a is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 4 is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 4a is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 5 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, optionally substituted phenyl, or together with R 5 or together with R 7 can form an optionally substituted polycyclic ring;
  • R 7 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R 6 or together with R 8 can form an optionally substituted polycyclic ring;
  • R 8 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R 7 or together with R 9 can form an optionally substituted polycyclic ring;
  • R 9 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, optionally substituted phenyl, or together with R 8 can form a polycyclic ring;
  • R 10 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R 11 can form a polycyclic ring;
  • R 11 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, N0 2 , -NHC(0)CF 3 , -S(0) 2 NMe 2 , optionally substituted phenyl, or together with R 10 or together with R 12 can form a polycyclic ring;
  • R 12 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, halogen optionally substituted phenyl, or together with R 11 or together with R 13 can form a polycyclic ring;
  • R 13 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R 12 can form a polycyclic ring;
  • R 14 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 15 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , N0 2 , -CF 3 , - S(0) x R 29 , -P(0)(0H) 2 , C(R 28 )(R 29 )C(0)NR 35 0R 34 , -0P(0)(0H) 2 , -SR 31 , pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, phenyl, naphthalene, cyclohexene, F, Cl, Br, or I;
  • R 21 is OF1, OR 26 , NR 23 R 24 , or optional
  • R 22 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 23 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 24 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 25 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, OR 22 , or - NR 23 R 24 ;
  • R 26 is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 27 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 28 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 29 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 30 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 31 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 32 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 33 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 34 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 35 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 36 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • x is 1 or 2;
  • X 1 is Cl
  • X 2 is Cl.
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IAB1C3),
  • X 3 is O or S
  • X 4 is O or S
  • X is -CR la R 2a -;
  • R Ia is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl or optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C 1 -C 6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, - S(0) x R 25 , -P(0)(0H)2, -0P(0)(0H)2, or -SR 27 ;
  • R 2a is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Ci-C 6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , N0 2 , -CF 3 , - S(0)xR 25 , -P(0)(0H)2, -0P(0)(0H) 2 , or -SR 27 ;
  • a is 1 or 2;
  • Y is -CR Ib R 2b -;
  • R lb is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, - S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , or -SR 27 ;
  • R 2b is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO
  • b 0, 1 or 2;
  • W is O, halogen, NR 20 or S;
  • R 3 is H, optionally substituted C e alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, - S(0) x R 25 , -P(0)(0H)2, -0P(0)(0H) 2 , or -SR 27 ;
  • R 3a is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Ci-Ce heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF 3 , - S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , or -SR 27 ;
  • R 4 is H, optionally substituted Ci_ 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , N0 2 , -CF3, - S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , or together with R 4a forms an optionally substituted spiro cyclohexyl or adamantyl;
  • R 4a is H, optionally substituted Ci- 6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , NO2, -CF3, - S(0) x R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 27 , or together with R 4 forms an optionally substituted spiro cyclohexyl or adamantyl;
  • R 5 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 6 can form an optionally substituted polycyclic ring;
  • R 6 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 5 or together with R 7 can form an optionally substituted polycyclic ring;
  • R 7 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 6 or together with R 8 can form an optionally substituted polycyclic ring
  • R 8 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 7 or together with R 9 can form an optionally substituted polycyclic ring
  • R 9 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 8 can form a polycyclic ring;
  • R 10 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 1 1 can form a polycyclic ring;
  • R 11 is H, optionally substituted Ci- 6 alkyl, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , N0 2 , -CPs, -S(0) X R 25 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -NHC(0)CF 3 , -SR 27 , optionally substituted phenyl, or together with R 10 or together with R 12 can form a polycyclic ring;
  • R 12 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 11 or together with R 13 can form a polycyclic ring;
  • R 13 is H, optionally substituted Ci- 6 alkyl, halogen, optionally substituted phenyl, or together with R 12 can form a polycyclic ring;
  • R 14 is H, or optionally substituted Ci- 6 alkyl
  • R 15 is optionally substituted Ci_ 6 alkyl, -C(R 28 )(R 29 )COOR 30 , -C(R 28 )(R 29 )C(0)H, - C(R 28 )(R 29 )C(0)R 31 , -C(R 28 )(R 29 )CR 32 (OR 33 )(OR 34 ), -C(R 28 )(R 29 )C(0)NR 35 R 36 , - C(R 28 )(R 29 )C(0)NR 35 0R 34 , - C(0)R 21 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted phenyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, or together with R 20 can form an optionally substituted heterocyclic ring;
  • R 16 is H, optionally substituted Cue alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , N0 2 , -CF 3 , -S(0) X R 29 , -P(0)(0H) 2 , -0P(0)(0H) 2 -SR 31 , optionally substituted heterocycle, optionally substituted C 3 -s cycloalkyl, optionally substituted phenyl or together with R 17 can form an optionally substituted polycyclic ring;
  • R 17 is H, optionally substituted Ci- 6 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , N0 2 , -CPs, -S(0) X R 29 , -P(0)(0H) 2 , -0P(0)(0H) 2 -SR 31 , optionally substituted phenyl or optionally substituted C 3-8 cycloalkenyl, or together with R 16 or together with R 18 can form an optionally substituted polycyclic ring;
  • R 18 is H, optionally substituted Ci- 6 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , N0 2 , -CF 3 , -S(0) X R 29 , -P(0)(0H) 2 , -0P(0)(0H) 2, -SR 31 , optionally substituted phenyl or together with R 17 or together with R 19 can form an optionally substituted polycyclic ring;
  • R 19 is H, optionally substituted Ci- 6 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)xR 29 , -P(0)(0H)2, -0P(0)(0H)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted phenyl or optionally substituted C3-8 cycloal
  • R 20 is H, optionally substituted Ci- 6 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted phenyl, or together with R 15 can form an optionally substituted heterocyclic ring;
  • R 21 is OH, OR 26 , NR 23 R 24 , or optionally substituted Ci- 6 alkyl;
  • R 22 is H, or optionally substituted Ci- 6 alkyl
  • R 23 is H, or optionally substituted Ci- 6 alkyl
  • R 24 is H, or optionally substituted Ci- 6 alkyl
  • R 25 is H, optionally substituted Ci- 6 alkyl, OR 22 , or - NR 23 R 24 ;
  • R 26 is optionally substituted Ci- 6 alkyl
  • R 27 is H, or optionally substituted Ci- 6 alkyl
  • R 28 is H, or optionally substituted Ci- 6 alkyl
  • R 29 is H, or optionally substituted Ci- 6 alkyl
  • R 30 is H, or optionally substituted Ci 6 alkyl
  • R 31 is H, or optionally substituted Ci- 6 alkyl
  • R 32 is H, or optionally substituted Ci- 6 alkyl
  • R 33 is H, or optionally substituted Ci- 6 alkyl
  • R 34 is H, or optionally substituted Ci- 6 alkyl
  • R 35 is H, or optionally substituted Ci- 6 alkyl
  • R 36 is H, or optionally substituted Ci- 6 alkyl
  • x is 1 or 2;
  • X 1 is halogen
  • X 2 is halogen
  • the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IAB1C3), wherein:
  • X 3 is S
  • X 4 is S; X is -CR la R 2a -;
  • R la is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR 23 R 24 , F, Cl, Br, or I;
  • R 2a is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR 23 R 24 , F, Cl, Br, or I;
  • a 2;
  • Y is -CR lb R 2b - ;
  • R lb is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR 23 R 24 , F, Cl, Br, or I;
  • R 2b is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR 23 R 24 , F, Cl, Br, or I;
  • b 0, 1 or 2;
  • W is O
  • R 3 is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 3a is El, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 4 is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 4a is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 5 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, optionally substituted phenyl, or together with R 6 can form an optionally substituted polycyclic ring;
  • R 6 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R 5 or together with R 7 can form an optionally substituted polycyclic ring;
  • R 7 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R 6 or together with R 8 can form an optionally substituted polycyclic ring;
  • R 8 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R 7 or together with R 9 can form an optionally substituted polycyclic ring;
  • R 9 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, optionally substituted phenyl, or together with R 8 can form a polycyclic ring;
  • R 10 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R 11 can form a polycyclic ring;
  • R 11 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, halogen, - C(0)R 21 , - OR 22 , CN, - NR 23 R 24 , N0 2 , - CF 3 , -S(0) X R 25 , -P(0)(0H)2, -0P(0)(0H) 2 , -NHC(0)CF 3 , -SR 27 , optionally substituted cyclopentyl, optionally substituted cyclohexyl, optionally substituted benzyl, optionally substituted phenyl, or together with R 10 or together with R 12 can form a polycyclic ring;
  • R 12 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, halogen, optionally substituted phneyl, or together with R 11 or together with R 13 can form a polycyclic ring;
  • R 13 is H, optionally substituted Ci- 6 alkyl, optionally substituted phenyl, or together with R 12 can form a polycyclic ring;
  • R 14 is H, or optionally substituted Ci-6 alkyl
  • R 15 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , N0 2 , -CF 3 , - S(0) x R 29 , -P(0)(0H) 2 , -0P(0)(0H) 2 , -SR 31 , pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, phenyl, naphthalene, cyclohexene, F, Cl, Br, or I;
  • R 16 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, Cl, Br, I, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0) x R 29 , -P(0)(0H) 2 , -0P(0)(0FI)2 , -SR 31 , pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, naphthalene, cyclohexene, optionally substituted phenyl or together with R 17 can form an optionally substituted polycyclic ring;
  • R 17 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, Cl, Br, I, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0) x R 29 , -P(0)(0H) 2 , -0P(0)(0H) 2, -SR 31 , pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, naphthalene, cyclohexene, optionally substituted phenyl, or together with R 16 or together with R 18 can form an optionally substituted polycyclic ring;
  • R 18 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, Cl, Br, I, - C(0)R 2S , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0) x R 29 , -P(0)(OH) 2 , -0P(0)(0H) 2 -SR 31 , pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, naphthalene, cyclohexene, optionally substituted phenyl or together with R 17 or together with R 19 can form an optionally substituted polycyclic ring;
  • R 19 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, Cl, Br, I, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0) x R 29 , -P(0)(0F1) 2 , -0P(0)(0H) 2, -SR 31 , pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, naphthalene, cyclohexene, optionally substituted phenyl or together with R 18 can form an optionally substituted polycyclic ring;
  • R 21 is OH, OR 26 , NR 23 R 24 , or optionally substituted Ci- 6 alkyl;
  • R 22 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 23 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 24 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 25 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, OR 22 , or - NR 23 R 24 ;
  • R 26 is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 27 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 28 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 29 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu
  • R 30 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu
  • R 31 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 32 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 33 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 34 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 35 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • R 36 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
  • x is 1 or 2;
  • X 1 is Cl
  • X 2 is Cl.
  • the invention provides an olefin metathesis catalyst wherein the Moiety (A) is represented by:
  • the invention provides an olefin metathesis catalyst wherein the Moiety (B) is represented by:
  • the invention provides an olefin metathesis catalyst wherein the Moiety (C) is represented by:
  • the present invention concerns also processes for preparing the olefin metathesis catalysts described herein.
  • the olefin metathesis catalysts according to the invention can be prepared analogously to conventional methods as understood by the person skilled in the art of synthetic organic chemistry.
  • the reactions take place under degassed N2 at room temperature or at high temperature. Once the reaction is completed, the mixture is cooled to room temperature, the solvent is removed under high vacuum, and the residue is purified on a silica gel column and then recrystallized to afford the new olefin metathesis catalysts.
  • the olefin metathesis catalysts are typically added to a resin composition as a solid, a solution, or as a suspension.
  • a dispersing carrier such as mineral oil, paraffin oil, soybean oil, tri-Ao-propyl -benzene, or any hydrophobic liquid which has an appropriately high viscosity so as to permit effective dispersion of the catalyst(s), and which is inert and which has a sufficiently high boiling point so that is does not act as a low- boiling impurity in the olefin metathesis reaction.
  • Resin compositions that may be formed comprise one or more cyclic olefins, besides the olefin metathesis catalysts of the invention.
  • the cyclic olefin may generally be any strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a ROMP reaction either individually or as part of a ROMP cyclic olefin composition.
  • Such cyclic olefins may be optionally substituted, optionally heteroatom-containing, mono-unsaturated, di-unsaturated, or polyunsaturated C5 to C24 hydrocarbons that may be mono-, di ⁇ , or poly-cyclic.
  • bicyclic and polycyclic olefins thus include, without limitation,
  • DCPD dicyclopentadiene
  • trimer and other higher order oligomers of cyclopentadiene including without limitation tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer, and cyclopentadiene pentamer
  • ethylidenenorbornene dicyclohexadiene; norbornene; C2-C12 hydrocarbyl substituted norbornenes
  • cyclododecene 8-cyanotetracyclo dodecene; pentacyclopentadecene; pentacyclo hexadecene; bicyclo[2.2.1]hept-2-ene-5-phenoxymethyl; 2-ethylhexyl ester-bicyclo[2.2.
  • Fig. 1 shows the results of Ring-Closing Metathesis of diethyl 2,2- diallylmalonate.
  • the compounds AS9pl, AS28b7 and AS33M obtained in Examples 1, 2 and 3 were employed as catalysts.
  • Neutral alumina Brockmann I
  • Methyl oleate is run through a plug of the neutral alumina and stored over fresh activated neutral alumina for 3 days.
  • the reactions are run in a Fischer-porter flask with a dip-tube for taking aliquots under the conditions given in the equation above. Aliquots are diluted with hexane and cooled to -78 °C immediately and stored cold until analysis by gas chromatography.
  • the compounds AS9pl, AS28b7 and AS33M obtained in Examples 1, 2 and 3 are employed as catalysts, showing ethenolysis activity as in the reaction equation given above.

Abstract

This invention relates generally to olefin metathesis catalysts comprising cyclic alkyl amino carbenes, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals and pharmaceuticals.

Description

METAL ORGANIC COMPOUNDS
TECHNICAL FIELD
[0001] This invention relates generally to olefin metathesis catalysts comprising cyclic alkyl amino carbenes, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals and pharmaceuticals.
BACKGROUND
[0002] Since its discovery in the 1950s, olefin metathesis has emerged as a valuable synthetic method for the formation of carbon-carbon double bonds. Recent advances in applications to organic syntheses and polymer syntheses mostly rely on developments of well-defined olefin metathesis catalysts.
[0003] The technology of ruthenium metathesis catalysts has enabled the development of several research platforms including: ring opening metathesis polymerization (ROMP), ring opening cross metathesis (ROCM), cross metathesis (CM), ring closing metathesis (RCM).
[0004] The incorporation of N-Heterocyclic Carbene (NHC) ligands has played an essential role in the development of ruthenium metathesis catalysts. Metathesis catalysts, based on ruthenium, are known and have been studied.
[0005] However, there is an ongoing need for olefin metathesis catalysts, particularly ruthenium metathesis catalysts with improved characteristics which will further enable their use in a wider array of applications and olefin metathesis reactions, and for methods to prepare them.
SUMMARY OF THE INVENTION
[0006] To meet this need, the inventors have discovered various olefin metathesis catalysts, comprising cyclic alkyl amino carbenes, represented by the general structure of Formula (I):
Figure imgf000003_0001
wherein:
M is Ru or Os; typically, M is Ru;
L2 and L3 are independently neutral ligands;
m is 0, 1 or 2; generally, m is 0 or 1; typically, m is 0;
n is 0 or 1; generally, n is 0;
k is 0 or 1; generally, k is 1;
X1 and X2 are independently anionic ligands; generally, X1 and X2 are independently halogen, trifluoroacetate, per-fluorophenols, -NCO, -CN, -NCS, -N3; or X1 together with X2 can form a nitrate; typically, X1 and X2 are independently halogen, or -NCO;
R1 and R2 are independently selected from hydrogen, optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl; or any two or more of X1, X2, L2, L3, R1, and R2 are taken together to form one or more cyclic groups;
X is -CRlaR2a-;
a is 1 or 2;
Rla is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, -S(0)xR25, -P(0)(OH)2, - OP(0)(OH)2, -SR27, or together with R2a forms an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R3 or together with R4 forms an optionally substituted polycyclic ring; R2a is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, -S(0)xR25, -P(0)(0H)2, - 0P(0)(0H)2, -SR27, or together with Rla forms a spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R3 or together with R4 forms an optionally substituted polycyclic ring;
Y is -CRlbR2b-;
b is 0, 1 or 2;
Rlb is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, -S(0)xR25, -P(0)(0H)2, - 0P(0)(0H)2, -SR27, or together with R2b forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
R2b is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, -S(0)xR25, -P(0)(0H)2, - 0P(0)(0H)2, -SR27, or together with Rlb forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
R3 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0f[)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with Rla or together with R2a can form an optionally substituted polycyclic ring, or together with R3a can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl;
R3a is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, - CFs, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with Rla or together with R2a can form an optionally substituted polycyclic ring, or together with R3 can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl; R4 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with Rla or together with R2a can form an optionally substituted polycyclic ring, or together with R4a can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl;
R4a is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, - CF3, - S(0)xR25, -P(0)(0H)2, -OP(0)(OH)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with Rla or together with R2a can form an optionally substituted polycyclic ring, or together with R4 can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl;
R5 is H, optionally substituted Ci-24 alkyl, halogen- C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0F1)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkcnyl, or together with R6 can form an optionally substituted polycyclic ring;
R6 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R5 or together with R7 can form an optionally substituted polycyclic ring;
R7 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R6 or together with R8 can form an optionally substituted polycyclic ring;
R8 is H, optionally substituted Ci-24 alkyl, halogen- C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R7 or together with R9 can form an optionally substituted polycyclic ring; R9 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R8 can form a polycyclic ring;
R21 is OH, OR26, NR23R24, optionally substituted C1-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R22 is H, optionally substituted C i-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R23 is H, optionally substituted C i-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
cycloalkenyl;
R24 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
cycloalkenyl;
R25 is H, optionally substituted Ci-24 alkyl, OR22, - NR23R24, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R26 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
cycloalkenyl;
R27 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
cycloalkenyl;
x is 1 or 2; and with the provisos
a. when a is 2, then the "X-X" bond can be saturated or unsaturated;
b. when b is 2, the "Y-Y" bond can be saturated or unsaturated;
c. when a is 2, and the "X-X" bond is unsaturated, then R2a is nil;
d. when b is 1 , then R3a and R4a are both nil;
e. when b is 2, then R3a and R4a are both nil; f. when b is 2, and the "Y-Y" bond is unsaturated, then R2b is nil.
[0007] In one embodiment, the invention provides a method of synthesizing the olefin metathesis catalysts of the invention.
[0008] In one embodiment, the invention provides a method of using the olefin metathesis catalysts of the invention in metathesis reactions. The olefin metathesis catalysts of the invention are of particular benefit for use in metathesis reactions, such as ring opening metathesis polymerization reactions, ring-opening cross metathesis reactions, cross metathesis reactions, ring-closing metathesis reactions, self-metathesis reactions, as well as combinations of such metathesis reactions.
[0009] The olefin metathesis catalysts of the invention are also key intermediates in the synthesis of a variety of ruthenium olefin metathesis catalysts.
[0010] These and other aspects of the present invention will be apparent to the skilled artisan in light of the following detailed description and examples. Furthermore, it is to be understood that none of the embodiments or examples of the invention described herein are to be interpreted as being limiting.
DETAILED DESCRIPTION
[0011] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the meanings as described herein.
[0012] The term "alkyl" as used herein, refers to a linear, branched, saturated hydrocarbon group typically containing 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms: such as methyl (Me), ethyl (Et), n-propyl (Pr or n-Pr), isopropyl (i-Pr), n-butyl (Bu or n-Bu), isobutyl (i-Bu), t-butyl (t-Bu), octyl (Oct), decyl, and the like.
[0013] The term "cycloalkyl" refers to a cyclic alkyl group, can be monocyclic, bicyclic or polycyclic, typically having 3 to 10, preferably 5 to 7, carbon atoms, generally, cycloalkyl groups are cyclopentyl (Cp), cyclohexyl (Cy), adamantly.
[0014] The term "substituted alkyl" refers to alkyl substituted with one or more substituent groups, and the terms "heteroatom-containing alkyl" and "heteroalkyl" refer to alkyl in which at least one carbon atom is replaced with a heteroatom.
[0015] The term "alkylene" as used herein refers to a difunctional linear, branched alkyl group, where "alkyl" is as defined above. [0016] The term "alkenyl" as used herein refers to a linear, branched hydrocarbon group of 2 to 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, iso- propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, and the like. Preferred alkenyl groups herein contain 2 to 12 carbon atoms, more preferred alkenyl groups herein contain 2 to 6 carbon atoms.
[0017] The term "substituted alkenyl" refers to alkenyl substituted with one or more substituent groups, and the terms "heteroatom-containing alkenyl" and "heteroalkenyl" refer to alkenyl in which at least one carbon atom is replaced with a heteroatom.
[0018] The term "cycloalkenyl" refers to a cyclic alkenyl group, preferably having 3 to 8 carbon atoms.
[0019] The term "alkenylene" as used herein refers to a difunctional linear, branched, where "alkenyl" is as defined above.
[0020] The term "alkynyl" as used herein refers to a linear or branched hydrocarbon group of 2 to 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to 12 carbon atoms, more preferred alkynyl groups herein contain 2 to 6 carbon atoms.
[0021] The term "substituted alkynyl" refers to alkynyl substituted with one or more substituent groups, and the terms "heteroatom-containing alkynyl" and "heteroalkynyl" refer to alkynyl in which at least one carbon atom is replaced with a heteroatom.
[0022] The term "alkynylene" as used herein refers to a difunctional alkynyl group, where "alkynyl" is as defined above.
[0023] The term "alkoxy" as used herein refers to an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy" group may be represented as -O-alkyl where "alkyl" is as defined above. Analogously, "alkenyloxy" refer to an alkenyl group bound through a single, terminal ether linkage, and "alkynyloxy" refers to an alkynyl group bound through a single, terminal ether linkage.
[0024] The term "aryl" as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 6 to 10 carbon atoms. Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl (Ph), naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, phenanthryl and the like.
[0025] "Substituted aryl" refers to an aryl moiety substituted with one or more substituent groups, and the terms "heteroatom containing aryl" and "heteroaryl" refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail herein.
[0026] The term "aryloxy" as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein "aryl" is as defined above. An "aryloxy" group may be represented as -O-aryl where aryl is as defined above. Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 6 to 10 carbon atoms. Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p- halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy- phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.
[0027] The term "alkaryl" refers to an aryl group with an alkyl substituent, and the term "aralkyl" refers to an alkyl group with an aryl substituent, wherein "aryl" and "alkyl" are as defined above. Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms. Alkaryl groups include, without limitation, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7- dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta- 1,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl- butyl, 5-phenyl-pentyl, 4-phenyl cyclohexyl, 4-benzylcyclohexyl, 4-phenyl cyclohexylmethyl, 4- benzylcyclohexylmethyl, and the like.
[0028] The terms "alkaryloxy" and "aralkyloxy" refer to substituents of the formula -OR wherein R is alkaryl or aralkyl, respectively, as defined herein.
[0029] The term "acyl" refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, - (CO)-aralkyl, -(CO)-alkaryl, -(CO)-alkenyl, or -(CO)-alkynyl, and the term "acyloxy" refers to substituents having the formula -0(CO)-alkyl, -0(CO)-aryl, -0(CO)-aralkyl, -0(CO)-alkaryl, - 0(CO)-alkenyl, or -(CO)-alkynyl wherein "alkyl," "aryl", "aralkyl", "alkaryl", "alkenyl", and "alkynyl" are as defined above. The acetoxy group (-0(CO)CH3, often abbreviated as -OAc) is a common example of an acyloxy group. [0030] The terms "cyclic" and "ring" refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic. The term "alicyclic" is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic or polycyclic.
[0031] The term "polycyclic ring" refers to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that have at least two closed rings tethered, fused, linked via a single bond or bridged. Polycyclic rings include without limitation naphthyl, biphenyl, phenanthryl and the like.
[0032] The term "spiro compound" refers to a chemical compound, that presents a twisted structure of two or more rings (a ring system), in which 2 or 3 rings are linked together by one common atom,
[0033] The terms "halo" and "halogen" and "halide" are used in the conventional sense to refer to a fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) substituent.
[0034] "Hydrocarbyl" refers to univalent hydrocarbyl moieties containing 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like. "Substituted hydrocarbyl" refers to hydrocarbyl substituted with one or more substituent groups.
[0035] "Hydrocarbylene" refers to divalent hydrocarbyl moieties containing 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, formed by removal of two hydrogens from a hydrocarbon. "Substituted hydrocarbylene" refers to hydrocarbylene substituted with one or more substituent groups.
[0036] The term "heteroatom-containing" as in a "heteroatom-containing hydrocarbyl group" refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur. The term "heteroatom-containing hydrocarbylene" and heterohydrocarbylene" refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom. Similarly, the term "heteroalkyl" refers to an alkyl substituent that is heteroatom-containing, the term "heterocyclic" refers to a cyclic substituent that is heteroatom-containing, the terms "heteroaryl" and "heteroaromatic" respectively refer to "aryl" and "aromatic" substituents that are heteroatom-containing, and the like. It should be noted that a "heterocyclic" group or compound may or may not be aromatic, and further that
"heterocycles" may be monocyclic, bicyclic, or polycyclic as described above with respect to the term "aryl." Examples of heteroalkyl groups include without limitation alkoxyaryl,
alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include without limitation pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples of heteroatom-containing alicyclic groups include without limitation pyrrolidino, morpholino, piperazino, piperidino, etc.
[0037] In addition, the aforementioned substituent groups may, if a particular group permits, be further substituted with one or more additional substituent groups or with one or more hydrocarbyl moieties such as those specifically enumerated above. Analogously, the above mentioned hydrocarbyl moieties may be further substituted with one or more substituent groups or additional hydrocarbyl moieties such as those specifically mentioned above. Analogously, the above-mentioned hydrocarbylene moieties may be further substituted with one or more substituent groups or additional hydrocarbyl moieties as noted above.
[0038] By "substituted" as in "substituted hydrocarbyl", "substituted alkyl", "substituted aryl", and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation groups such as halo, hydroxyl, sulfhydryl, C1-C24 alkoxy, C2-C24 alkenyloxy, C2-C24 alkynyloxy, C5-C24 aryloxy, C6-C24 aralkyloxy, C6-C24 alkaryloxy, acyl (including C2-C24 alkylcarbonyl (-CO-alkyl) and C6-C24 arylcarbonyl (-CO-aryl)), acyloxy (-0- acyl, including C2-C24 alkylcarbonyloxy (-O-CO-alkyl) and C6-C24 arylcarbonyloxy (-O-CO- aryl)), C2-C24 alkoxycarbonyl (-(CO)-O-alkyl), C6-C24 aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-CO)-X where X is halo), C2-C24 alkylcarbonato (-O-(CO)-O-alkyl), C6-C24 arylcarbonato (-O-(CO)-O-aryl), carboxylic acid (-COOH), carbamoyl (-(CO)-NH2), mono-(Ci- C24 alkyl)-substituted carbamoyl (-(CO)-NH(CI-C24 alkyl)), di-(Ci-C24 alkyl)-substituted carbamoyl (-(CO)-N(CI-C24 alkyl)2), mono-(Ci-C24 haloalkyl)-substituted carbamoyl (-(CO)- NH(CI-C24 haloalkyl)), di-(Ci-C24 haloalkyl)-substituted carbamoyl (-(CO)-N(CI-C24 haloalkyl)2), mono-(Cs-C24 aryl)-substituted carbamoyl (-(CO)-NH-aryl), di-(Cs-C24 aryl)- substituted carbamoyl (-(CO)-N(C5-C24 aryl)2), N(CI-C24 alkyl)(C5-C24 aryl)-substituted carbamoyl (-(CO)-N(CI-C24 alkyl)(Cs-C24 aryl), thiocarbamoyl (-(CS)-NH2), mono-(Ci-C24 alkyl)-substituted thiocarbamoyl (-(CS)-NH(CI-C24 alkyl)), di-(Ci-C24 alkyl)-substituted thiocarbamoyl (-(CS)-N(CI-C24 alkyl)2), mono-(Cs-C24 aryl)-substituted thiocarbamoyl (-(CS)- NH-aryl), di-(Cs-C24 aryl)-substituted thiocarbamoyl (-(CS)-N(Cs-C24 aryl)2), N(CI-C24
alkyl)(C5-C24 aryl)-substituted thiocarbamoyl (-(CS)-N(CI-C24 alkyl)(Cs-C24 aryl), carbamido (- NH-(CO)-NH2), cyano (-CºN), cyanato (-0-CºN), thiocyanato (-S-CºN), isocyanate (-NCO), thioisocyanate (-NCS), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono-(Ci-C24 alkyl)-substituted amino (-NH(CI-C24 alkyl), di-(Ci-C24 alkyl)-substituted amino ((-N(CI-C24 alkyl)2), mono-(Cs-C24 aryl)-substituted amino (-NH(C5-C24 aryl), di-(C5-C24 aryl)-substituted amino (-N(C5-C24 aryl)2), C2-C24 alkylamido (-NH-(CO)-alkyl), C6-C24 arylamido (-NH-(CO)- aryl), imino (-CRNH where, R includes without limitation H, C1-C24 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), C2-C20 alkylimino (-CRN(alkyl), where R includes without limitation H, C1-C24 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), arylimino (- CRN(aryl), where R includes without limitation H, C1-C20 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6- C24 aralkyl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-S(0)20H), C1-C24 alkylsulfanyl (-S-alkyl; also termed "alkylthio"), C5-C24 arylsulfanyl (-S-aryl; also termed "arylthio"), C1-C24 alkylsulfinyl (-(SO)-alkyl), CS-C24 arylsulfinyl (-(SO)-aryl), C1-C24 alkylsulfonyl (-S02-alkyl), C1-C24 monoalkylaminosulfonyl (-S02-N(H) alkyl), C1-C24 dialkylaminosulfonyl (-SO2- N(alkyl)2), C5-C24 arylsulfonyl (-S02-aryl), boryl (-BH2), borono (-B(OH)2), boronato (-B(OR)2 where R includes without limitation alkyl or other hydrocarbyl), phosphono (-P(0)(0H)2), phospho (-PO2), phosphino (-PH2), silyl (-S1R3 wherein R is H or hydrocarbyl), and silyloxy (-0- silyl); hydrocarbyl moieties C1-C24 alkyl (preferably C1-C12 alkyl, more preferably C1-C6 alkyl), C2-C24 alkenyl (preferably C2-C12 alkenyl, more preferably C2-C6 alkenyl), C2-C24 alkynyl (preferably C2-C12 alkynyl, more preferably C2-C6 alkynyl), C5-C24 aryl (preferably C6-C10 aryl), C6-C24 alkaryl (preferably C6-C16 alkaryl), or C6-C24 aralkyl (preferably C6-C16 aralkyl).
[0039] By "functionalized" as in "functionalized hydrocarbyl", "functionalized alkyl", "functionalized olefin", "functionalized cyclic olefin", and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one H atom bound to a carbon (or other) atom is replaced with one or more functional group(s) such as those described hereinabove. The term "functional group" is meant to include any functional species that is suitable for the uses described herein. In some cases, the terms "substituent" and "functional group" are used interchangeably. [0040] "Optional" or "optionally" means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase "optionally substituted" means that a non- hydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non- hydrogen substituent is not present.
[0041] The term "nil", as used herein, means absent or nonexistent.
[0042] The term "sulfhydryl" as used herein, represents a group of formula SH".
[0043] The term "hydroxyl" as used herein, represents a group of formula "-OH".
[0044] The term "carbonyl" as used herein, represents a group of formula "-C(O)- ".
[0045] The term "ketone" as used herein, represents an organic compound having a carbonyl group linked to a carbon atom such as -C(0)Rx, wherein Rx can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0046] The term "ester" as used herein, represents an organic compound having a carbonyl group linked to a carbon atom such as -C(0)ORx wherein Rx can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0047] The term "amine" as used herein, represents a group of formula "-NRxRy ", wherein Rx and Ry can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0048] The term "carboxyl" as used herein, represents a group of formula "-C(0)0-".
[0049] The term "sulfonyl" as used herein, represents a group of formula "-SO2 ".
[0050] The term "sulfate" as used herein, represents a group of formula "-0-S(0)2-0-".
[0051] The term "sulfonate" as used herein, represents a group of the formula "-S(0)2-0-".
[0052] The term "amide" as used herein, represents a group of formula "-C(0)NRxRy", wherein Rx and Ry can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0053] The term "sulfonamide" as used herein, represents a group of formula "-S(0)2NRxRy" wherein Rx and Ry can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
[0054] The term "sulfoxide" as used herein, represents a group of formula "-S(O)- ".
[0055] The term "phosphonic acid" as used herein, represents a group of formula "-P(0)(OH)2". [0056] The term "phosphoric acid" as used herein, represents a group of formula
Figure imgf000014_0001
0P(0)(0H)2".
[0057] The term "sulphonic acid" as used herein, represents a group of formula "-S(0)20H".
[0058] The formula "H", as used herein, represents a hydrogen atom.
[0059] The formula "O", as used herein, represents an oxygen atom.
[0060] The formula "N", as used herein, represents a nitrogen atom.
[0061] The formula "S", as used herein, represents a sulfur atom.
[0062] Functional groups may be protected in cases where the functional group interferes with the metal carbene olefin metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 5th Ed. (New York: Wiley, 2014). Examples of protecting groups include acetals, cyclic acetals, boronate esters (boronates), cyclic boronate esters (cyclic boronates), carbonates, or the like. Examples of protecting groups include cyclic acetals or cyclic boronate esters.
METAL CARBENE OLEFIN METATHESIS CATALYSTS OF THE INVENTION
[0063] In one embodiment, the invention provides olefin metathesis catalysts, represented by the structure of Formula (I), as described herein.
[0064] Formula (I) is formed by different moieties, as shown in Scheme (1), below:
Figure imgf000014_0002
Scheme (1)
[0065] In one embodiment, the invention provides a metal carbene olefin metathesis catalyst, represented by the structure of Formula (II), as represented below:
Figure imgf000015_0001
Formula (II)
[0066] Formula (II) is formed by different moieties, as shown in Scheme (2), below:
Figure imgf000015_0002
Scheme (2)
[0067] Table (1) illustrates possible moieties which form general Formula (I) and general Formula (II). Depending on the values of "a" and "b", substructures of the Moiety (A), are exemplified in Table (1). Depending on the values of X1 and X2, substructures of Moiety (B) are exemplified in Table (1). Depending on the values of R1 and R2, substructures of Moiety (C) are exemplified in Table (1). Any combination of a Moiety (A), Moiety (B) and Moiety (C) can form a ruthenium carbene olefin metathesis catalyst of the invention, according to Formula (I) and Formula (II).
Figure imgf000016_0001
Figure imgf000017_0001
[0068] The values of the substituents described in Table (1) are as follows:
M is Ru;
X1 is an anionic ligand; generally, X1 is halogen, trifluoroacetate, per-fluorophenols, - NCO, -CN, -NCS, -N3, ; or together with X2 can form a nitrate; typically; X1 is halogen, or - NCO; specifically, in the present case X1 is Cl;
X2 is an anionic ligand; generally, X2 is halogen, trifluoroacetate, per-fluorophenols, - NCO, -CN, -NCS, -N3; or together with X1 can form a nitrate; typically, X2 is halogen, or -NCO; specifically, in the present case X2 is Cl; or X1 and X2 together with the ruthenium can form
Figure imgf000018_0001
R1 is hydrogen, optionally substituted hydrocarbyl, or optionally substituted heteroatom- containing hydrocarbyl; generally, R1 is H; or together with R2 can form a substituted indenylidene;
R2 is hydrogen, optionally substituted hydrocarbyl, optionally substituted heteroatom- containing hydrocarbyl; generally, R2 is optionally substituted C2-24 alkenyl or optionally substituted phenyl or together with R1 can form a substituted indenylidene;
X is -CRlaR2a-;
a is 1 or 2; generally, a is 2;
Rla is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, -S(0)xR25, -P(0)(OH)2, - OP(0)(OH)2, -SR27, or together with R2a forms an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R3 or together with R4 forms an optionally substituted polycyclic ring;
R2a is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, - 0P(0)(0H)2, -SR27, or together with Rla forms a spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R3 or together with R4 forms an optionally substituted polycyclic ring;
Y is -CRlbR2b-;
b is 0, 1 or 2; generally, b is 0 or 1; typically, b is 0;
Rlb is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, -S(0)xR25, - P(0)(OH)2, -OP(0)(OH)2, -SR27, or together with R2b forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
R2b is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, - P(0)(OH)2, -OP(0)(OH)2, -SR27, or together with Rlb forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
R3 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0F1)2, -OP(0)(OH)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R3a can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or together with Rla or together with R2a can form an optionally substituted polycyclic ring;
R3a is FI, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0F1)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R3 can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or together with Rla or together with R2a can form an optionally substituted polycyclic ring;
R4 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21 , - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(OH)2, -OP(0)(OH)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R4a can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or together with Rla or together with R2a can form an optionally substituted polycyclic ring;
R4a is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R4 can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or together with Rla or together with R2a can form an optionally substituted polycyclic ring;
W is O, NR20 or S;
RI0 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with Rn can form a polycyclic ring;
R11 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -OP(0)(OH)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R10 or together with R12 can form a polycyclic ring;
R12 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO¾ -CF3, -S(0)XR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, -NHC(0)CF3, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R11 or together with R13 can form a polycyclic ring;
R13 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)XR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R12 can form a polycyclic ring;
R14 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl; R15 is H, optionally substituted Ci-24 alkyl, -C(R28)(R29)COOR30, -C(R28)(R29)C(0)H, - C(R28)(R29)C(0)R31, -C(R28)(R29)CR32(OR33)(OR34), -C(R28)(R29)C(0)NR35R36, - C(R28)(R29)C(0)NR350R34, - C(0)R21, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R20 can form an optionally substituted heterocyclic ring or is nil when W is halogen;
R16 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21 , - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R17 can form an optionally substituted polycyclic ring;
R17 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R16 or together with R18 can form an optionally substituted polycyclic ring;
R18 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24,
N02, -CF3, . S(0)xR25, -P(0)(0F1)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted Cs-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R17 or together with R19 can form an optionally substituted polycyclic ring;
R18a is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R16 can form an optionally substituted polycyclic ring;
R19 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21 , - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted Cs-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R18 can form an optionally substituted polycyclic ring.
R20 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R15 can form an optionally substituted heterocyclic ring; R21 is OH, OR26, NR23R24, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R22 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R23 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R24 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
x is 1 or 2;
R25 is H, optionally substituted Ci-24 alkyl, OR22, - NR23R24, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R26 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R27 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R28 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R29 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R19 can form an optionally substituted heterocyclic ring;
R30 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl; R31 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R32 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R33 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R34 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R35 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R36 is II, optionally substituted Ci-24 alkyl, - OR22, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
X3 is O or S; typically, X3 is S;
X4 is O or S; typically, X4 is S;
X5 is CN or NO2; typically, X5 is CN;
X6 is CN or NO2; typically, X6 is CN; and
with the provisos:
a. when a is 2, then the "X-X" bond can be saturated or unsaturated;
b. when b is 2, the "Y-Y" bond can be saturated or unsaturated;
c. when a is 2, and the "X-X" bond is unsaturated, then R2a is nil;
d. when b is 1, then R3a and R4a are both nil;
e. when b is 2, then R3a and R4a are both nil;
f. when b is 2, and the "Y-Y" bond is unsaturated, then R2b is nil. [0069] Therefore, the invention provides olefin metathesis catalysts, wherein the nomenclature of the olefin metathesis catalysts is determined by the combination of Moieties (A), (B), and (C) according to Table (1).
[0070] For example, olefin metathesis catalyst represented by the structure shown below is of general Formula (I) and is composed of Moiety (A13), Moiety (B2) and Moiety (C3), therefore it is assigned Formula (IA13B2C3):
Moiety (A13)
Figure imgf000024_0001
[0071] In another example, the olefin metathesis catalyst represented by the structure shown below, is of general Formula (II) and is composed of two Moieties (A9), Moiety (B4) and Moiety (C2), therefore it is assigned Formula (IIA9B4C2A9):
Moiety (A9)
Figure imgf000025_0001
Formula (IIA9B4C2A9)
[0072] Other examples of olefin metathesis catalysts of the invention are represented by the structures shown below, wherein the nomenclature was assigned as described herein:
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Formula (IA8B3C3) Formula (IA6B3C3)
Figure imgf000030_0001
[0073] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IAB4C3),
Figure imgf000030_0002
wherein:
X1 is halogen;
X2 is halogen;
X is -CRlaR2a-;
Rla is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl or optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27;
R2a is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H 2, or -SR27;
a is 1 or 2;
Y is -CRlbR2b-;
Rlb is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C\-Ce heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27;
R2b is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3,— S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27;
b is 0, 1 or 2;
R3 is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Ci-Ce heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H) , -OP(0)(OH)2, or -SR27;
R3a is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27; R4 is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27 , or together with R4a forms an optionally substituted spiro cyclohexyl or adamantyl;
R4a is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Ci-Ce heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H>2, -0P(0)(0H)2, -SR27, or together with R4 forms an optionally substituted spiro cyclohexyl or adamantyl;
R5 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R6 can form an optionally substituted polycyclic ring;
R6 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R5 or together with R7 can form an optionally substituted polycyclic ring;
R7 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R6 or together with R8 can form an optionally substituted polycyclic ring;
R8 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R7 or together with R9 can form an optionally substituted polycyclic ring;
R9 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R8 can form a polycyclic ring;
W is O, S, or NR20;
R10 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R11 can form a polycyclic ring;
R11 is FI, optionally substituted Ci-6 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted cyclohexyl, optionally substituted cyclopentyl, optionally substituted phenyl, optionally substituted benzyl or together with R10 or together with R12 can form a polycyclic ring;
R12 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R11 or together with R13 can form a polycyclic ring;
R13 is H, optionally substituted Ci-6 alkyl, optionally substituted phenyl, or together with R12 can form a polycyclic ring; R14 is H, or optionally substituted Ci-6 alkyl;
R15 is optionally substituted Ci-6 alkyl, -C(R28)(R29)COOR30, -C(R28)(R29)C(0)H, - C(R28)(R29)C(0)R31 , -C(R28)(R29)CR32(OR33)(OR34), -C(R28)(R29)C(0)NR35R36, - C(R28)(R29)C(0)NR350R34, C(R28)(R29)C(0)NR350R34, - C(0)R21, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted phenyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, or together with R20 can form an optionally substituted heterocyclic ring;
R20 is H, optionally substituted Ci-6 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted phenyl, or together with R15 can form an optionally substituted heterocyclic ring;
R21 is OH, OR26, NR23R24, or optionally substituted Ci-6 alkyl;
R22 is H, or optionally substituted Ci-6 alkyl;
R23 is H, or optionally substituted Ci-6 alkyl;
R24 is H, or optionally substituted Ci-6 alkyl;
R25 is H, or optionally substituted Ci-6 alkyl, OR22, - NR23R24;
R26 is optionally substituted Ci-6 alkyl;
R27 is H, or optionally substituted Ci-6 alkyl;
R28 is H, or optionally substituted Ci-6 alkyl;
R29 is H, or optionally substituted Ci-6 alkyl;
R30 is H, or optionally substituted Ci6 alkyl;
R31 is H, or optionally substituted Ci-6 alkyl;
R32 is H, or optionally substituted Ci-6 alkyl;
R33 is H, or optionally substituted Ci-6 alkyl;
R34 is H, or optionally substituted Ci-6 alkyl;
R35 is H, or optionally substituted Ci-6 alkyl;
R36 is H, or optionally substituted C 1-6 alkyl; and
x is 1 or 2.
[0074] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IAB4C3):
X is -CRlaR2a-; Rla is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR23R24, F, Cl, Br, or I;
R2a is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR23R24, F, Cl, Br, or I;
a is 2;
Y is -CRlbR2b-;
Rlb is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR23R24, F, Cl, Br, or I;
R2b is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, - R23R24, F, Cl, Br, or I;
b is 0, 1 or 2;
W is O;
R3 is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R3a is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R4 is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R4a is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R5 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, optionally substituted phenyl, or together with R5 or together with R7 can form an optionally substituted polycyclic ring;
R7 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R6 or together with R8 can form an optionally substituted polycyclic ring;
R8 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R7 or together with R9 can form an optionally substituted polycyclic ring;
R9 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, optionally substituted phenyl, or together with R8 can form a polycyclic ring;
R10 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R11 can form a polycyclic ring;
R11 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, N02, -NHC(0)CF3, -S(0)2NMe2, optionally substituted phenyl, or together with R10 or together with R12 can form a polycyclic ring;
R12 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, halogen optionally substituted phenyl, or together with R11 or together with R13 can form a polycyclic ring;
R13 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R12 can form a polycyclic ring;
R14 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu; R15 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, - C(0)R25, - OR26, CN, - NR27R28, N02, -CF3, - S(0)xR29, -P(0)(0H)2, C(R28)(R29)C(0)NR350R34, -0P(0)(0H)2, -SR31, pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, phenyl, naphthalene, cyclohexene, F, Cl, Br, or I; R21 is OF1, OR26, NR23R24, or optionally substituted Ci-6 alkyl;
R22 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R23 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R24 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R25 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, OR22, or - NR23R24;
R26 is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R27 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R28 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R29 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R30 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R31 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R32 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R33 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R34 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R35 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R36 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
x is 1 or 2;
X1 is Cl; and
X2 is Cl.
[0075] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IAB1C3),
Figure imgf000036_0001
X3 is O or S;
X4 is O or S;
X is -CRlaR2a-;
RIa is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl or optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27;
R2a is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Ci-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27;
a is 1 or 2;
Y is -CRIbR2b-;
Rlb is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27; R2b is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27;
b is 0, 1 or 2;
W is O, halogen, NR20 or S;
R3 is H, optionally substituted C e alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27;
R3a is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted Ci-Ce heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, or -SR27;
R4 is H, optionally substituted Ci_6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, or together with R4a forms an optionally substituted spiro cyclohexyl or adamantyl;
R4a is H, optionally substituted Ci-6 alkyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, halogen, optionally substituted phenyl, optionally substituted benzyl, optionally substituted C1-C6 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, NO2, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, or together with R4 forms an optionally substituted spiro cyclohexyl or adamantyl;
R5 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R6 can form an optionally substituted polycyclic ring;
R6 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R5 or together with R7 can form an optionally substituted polycyclic ring;
R7 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R6 or together with R8 can form an optionally substituted polycyclic ring; R8 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R7 or together with R9 can form an optionally substituted polycyclic ring;
R9 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R8 can form a polycyclic ring;
R10 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R1 1 can form a polycyclic ring;
R11 is H, optionally substituted Ci-6 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, N02, -CPs, -S(0)XR25, -P(0)(0H)2, -0P(0)(0H)2, -NHC(0)CF3, -SR27, optionally substituted phenyl, or together with R10 or together with R12 can form a polycyclic ring;
R12 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R11 or together with R13 can form a polycyclic ring;
R13 is H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl, or together with R12 can form a polycyclic ring;
R14 is H, or optionally substituted Ci-6 alkyl;
R15 is optionally substituted Ci_6 alkyl, -C(R28)(R29)COOR30, -C(R28)(R29)C(0)H, - C(R28)(R29)C(0)R31 , -C(R28)(R29)CR32(OR33)(OR34), -C(R28)(R29)C(0)NR35R36, - C(R28)(R29)C(0)NR350R34, - C(0)R21, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted phenyl, optionally substituted cyclopentyl, optionally substituted cyclohexyl, or together with R20 can form an optionally substituted heterocyclic ring;
R16 is H, optionally substituted Cue alkyl, halogen, - C(0)R25, - OR26, CN, - NR27R28, N02, -CF3, -S(0)XR29, -P(0)(0H)2, -0P(0)(0H)2 -SR31, optionally substituted heterocycle, optionally substituted C3-s cycloalkyl, optionally substituted phenyl or together with R17 can form an optionally substituted polycyclic ring;
R17 is H, optionally substituted Ci-6 alkyl, halogen, - C(0)R25, - OR26, CN, - NR27R28, N02, -CPs, -S(0)XR29, -P(0)(0H)2, -0P(0)(0H)2 -SR31, optionally substituted phenyl or optionally substituted C3-8 cycloalkenyl, or together with R16 or together with R18 can form an optionally substituted polycyclic ring;
R18 is H, optionally substituted Ci-6 alkyl, halogen, - C(0)R25, - OR26, CN, - NR27R28, N02, -CF3, -S(0)XR29, -P(0)(0H)2, -0P(0)(0H)2, -SR31, optionally substituted phenyl or together with R17 or together with R19 can form an optionally substituted polycyclic ring; R19 is H, optionally substituted Ci-6 alkyl, halogen, - C(0)R25, - OR26, CN, - NR27R28, NO2, -CF3, -S(0)xR29, -P(0)(0H)2, -0P(0)(0H)2, -SR31, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted phenyl or optionally substituted C3-8 cycloalkenyl, or together with R18 can form an optionally substituted polycyclic ring;
R20 is H, optionally substituted Ci-6 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted phenyl, or together with R15 can form an optionally substituted heterocyclic ring;
R21 is OH, OR26, NR23R24, or optionally substituted Ci-6 alkyl;
R22 is H, or optionally substituted Ci-6 alkyl;
R23 is H, or optionally substituted Ci-6 alkyl;
R24 is H, or optionally substituted Ci-6 alkyl;
R25 is H, optionally substituted Ci-6 alkyl, OR22, or - NR23R24;
R26 is optionally substituted Ci-6 alkyl;
R27 is H, or optionally substituted Ci-6 alkyl;
R28 is H, or optionally substituted Ci-6 alkyl;
R29 is H, or optionally substituted Ci-6 alkyl;
R30 is H, or optionally substituted Ci6 alkyl;
R31 is H, or optionally substituted Ci-6 alkyl;
R32 is H, or optionally substituted Ci-6 alkyl;
R33 is H, or optionally substituted Ci-6 alkyl;
R34 is H, or optionally substituted Ci-6 alkyl;
R35 is H, or optionally substituted Ci-6 alkyl;
R36 is H, or optionally substituted Ci-6 alkyl;
x is 1 or 2;
X1 is halogen; and
X2 is halogen.
[0076] In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IAB1C3), wherein:
X3 is S;
X4 is S; X is -CRlaR2a-;
Rla is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR23R24, F, Cl, Br, or I;
R2a is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR23R24, F, Cl, Br, or I;
a is 2;
Y is -CRlbR2b-;
Rlb is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR23R24, F, Cl, Br, or I;
R2b is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR23R24, F, Cl, Br, or I;
b is 0, 1 or 2;
W is O;
R3 is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R3a is El, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R4 is FI, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R4a is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R5 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, optionally substituted phenyl, or together with R6 can form an optionally substituted polycyclic ring;
R6 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R5 or together with R7 can form an optionally substituted polycyclic ring;
R7 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R6 or together with R8 can form an optionally substituted polycyclic ring;
R8 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R7 or together with R9 can form an optionally substituted polycyclic ring;
R9 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, optionally substituted phenyl, or together with R8 can form a polycyclic ring;
R10 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, optionally substituted phenyl, or together with R11 can form a polycyclic ring;
R11 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, halogen, - C(0)R21, - OR22, CN, - NR23R24, N02, - CF3, -S(0)XR25, -P(0)(0H)2, -0P(0)(0H)2, -NHC(0)CF3, -SR27, optionally substituted cyclopentyl, optionally substituted cyclohexyl, optionally substituted benzyl, optionally substituted phenyl, or together with R10 or together with R12 can form a polycyclic ring;
R12 is FI, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, halogen, optionally substituted phneyl, or together with R11 or together with R13 can form a polycyclic ring; R13 is H, optionally substituted Ci-6 alkyl, optionally substituted phenyl, or together with R12 can form a polycyclic ring;
R14 is H, or optionally substituted Ci-6 alkyl;
R15 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, - C(0)R25, - OR26, CN, - NR27R28, N02, -CF3, - S(0)xR29, -P(0)(0H)2, -0P(0)(0H)2, -SR31, pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, phenyl, naphthalene, cyclohexene, F, Cl, Br, or I;
R16 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, Cl, Br, I, - C(0)R25, - OR26, CN, - NR27R28, NO2, -CF3, -S(0)xR29, -P(0)(0H)2, -0P(0)(0FI)2, -SR31, pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, naphthalene, cyclohexene, optionally substituted phenyl or together with R17 can form an optionally substituted polycyclic ring;
R17 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, Cl, Br, I, - C(0)R25, - OR26, CN, - NR27R28, NO2, -CF3, -S(0)xR29, -P(0)(0H)2, -0P(0)(0H)2, -SR31, pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, naphthalene, cyclohexene, optionally substituted phenyl, or together with R16 or together with R18 can form an optionally substituted polycyclic ring;
R18 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, Cl, Br, I, - C(0)R2S, - OR26, CN, - NR27R28, NO2, -CF3, -S(0)xR29, -P(0)(OH)2, -0P(0)(0H)2 -SR31, pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, naphthalene, cyclohexene, optionally substituted phenyl or together with R17 or together with R19 can form an optionally substituted polycyclic ring;
R19 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, Cl, Br, I, - C(0)R25, - OR26, CN, - NR27R28, NO2, -CF3, -S(0)xR29, -P(0)(0F1)2, -0P(0)(0H)2, -SR31, pyridine, piperidine, imidazole, indolizine, indazole, cyclohexyl, naphthalene, cyclohexene, optionally substituted phenyl or together with R18 can form an optionally substituted polycyclic ring;
R21 is OH, OR26, NR23R24, or optionally substituted Ci-6 alkyl;
R22 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R23 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R24 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R25 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, OR22, or - NR23R24;
R26 is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R27 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R28 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R29 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu; R30 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R31 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R32 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R33 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R34 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R35 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
R36 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu;
x is 1 or 2;
X1 is Cl; and
X2 is Cl.
[0077] Examples of olefin metathesis catalysts represented by the structure of Formula (IA6B4C3), wherein: X1 = Cl, X2 = Cl, W = O, b = 0, a = 2, X = -CRlaR2a-, Rla = H, R2a = H, R6 = H, R8 = H, R10 = H, R11 = H, R12 = H, R13 = H, R14 = H, and R15 = i-Pr, are found in Table (2).
Figure imgf000042_0001
Table (2)
Examples of olefin metathesis catalysts represented by Formula (IA6B4C3)
Figure imgf000042_0002
Figure imgf000043_0001
Figure imgf000044_0001
[0078] Examples of olefin metathesis catalysts represented by the structure of Formula
(IA6B4C3), wherein, X1 = Cl, X2 = Cl, W = O, b = 0, a = 2, X = -CRlaR2a-, Rla = H, R2a = H, R6 = H, R8 = H, R10 = H, R11 = NHC(0)CF3, R12 = H, R13 = H, R14 = H, and R15 = i-Pr, are found in
Table (3).
Figure imgf000045_0001
Formula (IA6B4C3)
Table (3)
Examples of olefin metathesis catalysts represented by Formula (IA6B4C3)
Figure imgf000045_0002
Figure imgf000046_0001
Figure imgf000047_0002
[0079] Examples of olefin metathesis catalysts represented by the structure of Formula
(IA6B4C3), wherein, X1 = Cl, X2 = Cl, W = O, b = 0, a = 2, X = -CRlaR2a-, Rla = H, R2a = H, R6 = H, R8 = H, R10 = H, R11 = S(0)2NMe2, R12 = H, R13 = H, R14 = H, and R15 = i-Pr, are found in
Table (4).
Figure imgf000047_0001
Table (4)
Examples of olefin metathesis catalysts represented by Formula (IA6B4C3)
Figure imgf000047_0003
Figure imgf000048_0001
Figure imgf000049_0001
[0080] Examples of olefin metathesis catalysts represented by the structure of Formula (IA12B4C3), wherein: X1 = Cl, X2 = Cl, W = O, R15 = ?-Pr, b = 1, Y= -CRlbR2b-, a = 2, X = - CRlaR2a-, Rla = H, R2a = H, Rlb = H, R2b = H, R6 = H, R8 = H, R10 = H, R1 1 = H, R12 = H, R13 = H, R14 = H.
Figure imgf000050_0001
Formula (IA12B4C3)
Table (5)
Examples of olefin metathesis catalysts represented by Formula (IA12B4C3)
Figure imgf000050_0002
Figure imgf000051_0001
[0081] Examples of olefin metathesis catalysts represented by the structure of Formula (IA9B4C3) wherein: X1 = Cl, X2 = Cl, W = O, R15 = /-Pr, b = 2, Y= -CRlbR2b-, a = 2, X = - CRlaR2a-, Rla = H, R2a = H, Rlb = H, R2b = H, R6 = H, R8 = H, R10 = H, R11 = H, R12 = H, R13 = H, and R14 = H, are found in Table (6).
Figure imgf000052_0001
Formula (IA9B4C3)
Table (6)
Examples of olefin metathesis catalysts represented by Formula (IA9B4C3)
Figure imgf000052_0002
Figure imgf000053_0002
[0082] Examples of olefin metathesis catalysts represented by the structure of Formula
(IA6B1C3), wherein: = H, R8 = H, X3 = S, X4 =
Figure imgf000053_0001
, are found in Table (7).
Figure imgf000054_0001
Table (7)
Examples of olefin metathesis catalysts represented by Formula (IA6B1C3)
Figure imgf000054_0002
Figure imgf000055_0001
Figure imgf000056_0001
[0083] Examples of olefin metathesis catalysts represented by the structure of Formula (IA12B1C3), wherein: W = O, R15 = /-Pr, b = 1, a = 2, X = -CRI aR2a-, Rla = H, R2a = H, Y = - CRlbR2b~, Rlb = H, R2b = H, R6 = H, R8 = H, R10 = H, R1 1 = H, R12 = H, R13 = H, R14 = H, X3 = S, X4 = S, R17 = H, and R18 = H, are found in Table (8).
Figure imgf000057_0001
Table (8)
Examples of olefin metathesis catalysts represented by Formula (IA12B1C3)
Figure imgf000057_0002
Figure imgf000058_0001
Figure imgf000059_0002
[0084] Examples of olefin metathesis catalysts represented by the structure of Formula
(IA9B1C3), wherein: W = O, R15 = /-Pr, b = 2, Y= -CRlbR2b-, a = 2, X = -CRlaR2a-, Rla = H, R2a = H, Rlb = H, R2b = H, R6 = H, R8 = H, R10 = H, R11 = H, R12 = H, R13 = H, R14 = H, are found in
Table (9).
Figure imgf000059_0001
Table (9)
Examples of olefin metathesis catalysts represented by Formula (IA9B1C3)
Figure imgf000060_0001
Figure imgf000061_0001
[0085] Examples of olefin metathesis catalysts represented by the structure of Formula (IA6B2C3), wherein: W = O, R15 = i- Pr, b = 0, a = 2, X = -CRlaR2a-, Rla = H, R2a = H, R6 = H, RB = H R10 = H, R11 = H, R12 = H, R13 = H, R14 = H, X1 = Cl, X4 = S, R17 = H, and R18 = H are found in Table (10).
Figure imgf000062_0001
Table (10)
Examples of olefin metathesis catalysts represented by Formula (IA6B2C3)
Figure imgf000062_0002
Figure imgf000063_0001
Figure imgf000064_0001
[0086] Examples of olefin metathesis catalysts represented by the structure of Formula
(IA12B2C3) wherein: X1 = Cl, W = O, R15 = - Pr, b = 1, a = 2, X = -CRlaR2a-, Rla = H, R2a = H, Y = -CRlbR2b-, Rlb = H, R2b = H, R6 = H, R8 = H, R10 = H, Rn = H, R12 = H, R13 = H, R14 = H, X4 = S, R17 = H, R18 = H, and R18a = H are found in Table (11).
Figure imgf000065_0001
Table (11)
Examples of olefin metathesis catalysts represented by Formula (IA12B2C3)
Figure imgf000065_0002
Figure imgf000066_0001
Figure imgf000067_0002
[0087] Examples of olefin metathesis catalysts represented by the structure of Formula
(IA12B2C3) wherein: X1 = Cl, W = O, R15 = r'-Pr, b = 2, Y= -CRlbR2b-, a = 2, X = -CRlaR2a-, Ria = H, R 2a = H> Rib = H> R 2b = H, R6 = H, R8 = H, R10 = H, R11 = H, R12 = H, R13 = H, R14 = H,
X4 = S, R17 = H, R18 = H, and R18a = H, are found in Table (12).
Figure imgf000067_0001
Formula (IA12B2C3)
Table (12)
Examples of olefin metathesis catalysts represented by Formula (IA12B2C3)
Figure imgf000068_0001
Figure imgf000069_0001
[0088] Examples of olefin metathesis catalysts represented by the structure of Formula (IIA6B4C2A6), wherein:
Figure imgf000070_0001
H, and R8 = H are found in Table (13).
Figure imgf000070_0002
Formula (IIA6B4C2A6)
Table (13)
Examples of olefin metathesis catalysts represented by Formula (IIA6B4C2A6)
Figure imgf000070_0003
Figure imgf000071_0001
Figure imgf000072_0002
[0089] Examples of olefin metathesis catalysts represented by the structure of Formula (IIA6B4C1A6), wherein: X1 = Cl, X2 = Cl, b = 0, a = 2, X = -CRlaR2a-, Rla = H, R2a = H, R6 = H, and R8 = H are found in Table (14).
Figure imgf000072_0001
Table (14)
Examples of olefin metathesis catalysts represented by Formula (IIA6B4C1A6)
Figure imgf000072_0003
Figure imgf000073_0001
Figure imgf000074_0002
[0090] Examples of olefin metathesis catalysts represented by the structure of Formula (IIA6B4C3A6), wherein: X1 = Cl, X2 = Cl, b = 0, a = 2, X = -CRlaR2a-, Rla = H, R2a = H, R6 = H, R8 = H, R10 = H, R11 = H, R12 = H, R13 = H, R14 = H, W = O, and R15 = i-Pr, are found in
Table (15).
Figure imgf000074_0001
Formula (IIA6B4C3A6)
Table (15)
Examples of olefin metathesis catalysts represented by Formula (IIA6B4C3A6)
Figure imgf000074_0003
Figure imgf000075_0001
Figure imgf000076_0002
[0091] In one embodiment, the invention provides an olefin metathesis catalyst wherein the Moiety (A) is represented by:
Figure imgf000076_0001
Figure imgf000077_0001
[0092] In one embodiment, the invention provides an olefin metathesis catalyst wherein the Moiety (B) is represented by:
Figure imgf000078_0001
Figure imgf000079_0002
[0093] In one embodiment, the invention provides an olefin metathesis catalyst wherein the Moiety (C) is represented by:
Figure imgf000079_0001
Figure imgf000080_0001
[0094] The present invention concerns also processes for preparing the olefin metathesis catalysts described herein. The olefin metathesis catalysts according to the invention can be prepared analogously to conventional methods as understood by the person skilled in the art of synthetic organic chemistry.
[0095] The following synthetic schemes illustrate how the olefin metathesis catalysts of the invention can be generally synthesized.
Scheme 3
Figure imgf000080_0002
Scheme 5
Figure imgf000081_0001
Scheme 8
Figure imgf000082_0001
Scheme 11
[0096] Generally, the reactions take place under degassed N2 at room temperature or at high temperature. Once the reaction is completed, the mixture is cooled to room temperature, the solvent is removed under high vacuum, and the residue is purified on a silica gel column and then recrystallized to afford the new olefin metathesis catalysts.
[0097] At this stage, those skilled in the art will appreciate that many additional compounds that fall under the scope of the invention can be prepared by performing various common chemical reactions.
[0098] For example, the olefin metathesis catalysts are typically added to a resin composition as a solid, a solution, or as a suspension. When the olefin metathesis catalysts are added to a resin composition as a suspension, the olefin metathesis catalysts are suspended in a dispersing carrier such as mineral oil, paraffin oil, soybean oil, tri-Ao-propyl -benzene, or any hydrophobic liquid which has an appropriately high viscosity so as to permit effective dispersion of the catalyst(s), and which is inert and which has a sufficiently high boiling point so that is does not act as a low- boiling impurity in the olefin metathesis reaction.
OLEFINS
[0099] Resin compositions that may be formed, comprise one or more cyclic olefins, besides the olefin metathesis catalysts of the invention. The cyclic olefin may generally be any strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a ROMP reaction either individually or as part of a ROMP cyclic olefin composition. Such cyclic olefins may be optionally substituted, optionally heteroatom-containing, mono-unsaturated, di-unsaturated, or polyunsaturated C5 to C24 hydrocarbons that may be mono-, di~, or poly-cyclic.
[0100] Examples of bicyclic and polycyclic olefins thus include, without limitation,
dicyclopentadiene (DCPD); trimer and other higher order oligomers of cyclopentadiene including without limitation tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidenenorbornene; dicyclohexadiene; norbornene; C2-C12 hydrocarbyl substituted norbornenes; 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5- octyl-2-norbornene; 5-decyl-2 -norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5- ethylidene-2-norbornene; 5- Aopropenyl-2 -norbornene; 5 -propenyl -2 -norbornene; 5 -butenyl-2- norbornene; 5-tolyl-norbornene; 5-methyl-2 -norbornene; 5-ethyl-2 -norbornene; 5-/,vrbutyl-2- norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5- acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethyoxycarbonyl-l -norbornene; 5-methyl-5- methoxy-carbonylnorbornene; bicyclo[2.2.1]hept-2-ene-2 -carboxylic acid, 2-ethylhexyl ester; 5- cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo-5,6- dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxy carbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyl tetracyclododecene; 8- ethyltetracyclododecene; 8-methoxy carbonyltetracyclo dodecene; 8-methyl-8-tetra
cyclododecene; 8-cyanotetracyclo dodecene; pentacyclopentadecene; pentacyclo hexadecene; bicyclo[2.2.1]hept-2-ene-5-phenoxymethyl; 2-ethylhexyl ester-bicyclo[2.2. l]hept-5-ene-2- carboxylic acid; 2-hydroxyethyl ester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid; bicyclo[2.2.1] hept-5-ene-2 -methanol; bicyclo[2.2.1]hept-5-ene-2-heptanoic acid-methyl ester; bicyclo[2.2.1] hept-5-ene-2-hexanoic acid-methyl ester; l,4:5,8-dimethanonaphthalene, 2-hexyl-l,2,3,4,4a,5,8, 8a-octahydro; bicyclo[2.2.1]hept-5-ene-2-octanoic acid-methyl ester; l,4:5,8-dimethano naphthalene; 2-butyl-l,2,3,4,4a,5,8,8a-octahydro; ethylidenetetracyclododecene; 2-vinyl- l,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethano naphthalene; and the like, and their structural isomers, stereoisomers, and mixtures thereof.
EXAMPLES
6-membered CAAC Ruthenium complexes for Ethenolysis
Example 1
Figure imgf000086_0001
AS8a2 AS9pl C601
AS9pl. To a 4 mL vial in a glovebox loaded with salt AS8a2 (107.0 mg, 0.25 mmol, 3.0 equiv) was added a solution of Lithium bis(trimethylsilyl)amide (38.9 mg, 0.23 mmol, 2.8 equiv) in benzene (2.2 mL). The solution was stirred vigorously for 1 h at room temperature then filtered into a solution of C601 (50 mg, 0.083 mmol, 1.0 equiv) in benzene (0.5 mL). The solution was heated for 48 h at 45 °C then brought to room temperature and concentrated under reduced pressure. The residue was taken up in benzene (0.3 mL), the product precipitated with pentane (2 mL), and filtered to afford AS9pl (37 mg, 67%) as green solid. The product can be further purified by recrystallization from CH2Cl2/Ethanol.
!H NMR (benzene-rtd, 500 MHz): d =16.24 (s, 1H), 7.32 (dd, J = 8.3, 7.0 Hz, 1H), 7.23 (d, J= 7.7 Hz, 2H), 7.20 - 7.17 (m, 1H), 7.12 (dd, J = 7.5, 1.7 Hz, 1H), 6.70 (t, J = 7.4 Hz, 1H), 6.42 (d, J = 8.3 Hz, 1H), 4.60 (hept, J = 6.1 Hz, 1H), 4.26 - 4.19 (m, 2H), 3.29 (p, J = 6.6 Hz, 2H), 2.66 (d, J = 12.1 Hz, 2H), 2.08 - 2.02 (m, 2H), 1.93 (d, J = 13.4 Hz, 2H), 1.66 (d, J = 6.1 Hz, 6H), 1.74 - 1.52 (m, 4H), 1.17 - 1.10 (m, 12H), 1.01 (s, 3H), 1.00 (s, 3H). Example 2
Figure imgf000087_0001
AS28b7 To a 4 mL vial in a glovebox loaded with salt AS22a2 (41.4 mg, 0.10 mmol, 3.0 equiv) was added a solution of Lithium bis(trimethylsilyl)amide (15.6 mg, 0.09 mmol, 2.8 equiv) in benzene (0.6 mL). The solution was stirred vigorously for 1 h at room temperature then filtered into a solution of C601 (20 mg, 0.03 mmol, 1.0 equiv) in benzene (0.2 mL). The solution was heated for 72 h at 45 °C then brought to room temperature and concentrated under reduced pressure. The residue was taken up in benzene (0.1 mL), the product precipitated with pentane (2 mL), and then crystallized from CH2Cl /Ethanol to afford AS28b7 (5.3 mg,
25%) as a green-brown solid.
!H NMR (Benzene-r/6, 400 MHz): d = 16.20 (s, 1H), 7.31 (dd, J = 8.5, 6.8 Hz,IH), 7.25 - 7.21 (m, 2H), 7.20 - 7.17 (m, 1H), 7.12 - 7.06 (m, 1H), 6.69 (td, J = 7.4, 0.7 Hz, 1H), 6.41 (d, J=8.3 Hz, 1H), 4.59 (hept, J = 6.2 Hz, 1H), 3.84 (dq, J = 14.5, 7.3 Hz, 2H), 3.32 (hept, J = 6.5 Hz, 2H), 3.08 (dq, J = 14.6, 7.4 Hz, 2H), 1.96 - 1.91 (m, 2H), 1.66 - 1.63 (m, 2H), 1.64 (d, J = 6.1 Hz, 6H), 1.24 (t, J = 7.4 Hz, 6H), 1.13 (d, J = 6.7 Hz, 6H), 1.10 (s, 6H), 1.00 (d, J = 6.4 Hz, 6H). Example 3
A
Figure imgf000088_0001
AS33bl To a 4 mL vial in a glovebox loaded with salt AS19a5 (100.0 mg, 0.26 mmol, 2.2 equiv) was added a solution of Lithium bis(trimethylsilyl)amide (39 mg, 0.24 mmol, 2.0 equiv) in benzene (3.0 mL). The solution was stirred vigorously for 1 h at room temperature then filtered into a solution of C601 (70 mg, 0.117 mmol, 1.0 equiv) in benzene (0.5 mL). The solution was heated for 26 h at 45 °C then brought to room temperature and concentrated under reduced pressure. The residue was purified on a silica plug (benzene/diethyl ether) and crystallized from pentane to afford AS33bl (50 mg, 68%) as green solid.
MR (Benzene-r 6, 400 MHz): 5 = 16.16 (s, 1H), 7.24 - 7.20 (m, 5H), 7.14 - 7.10 (m,
2H) 6.71 (t, J = 7.4 Hz, 1H), 6.43 (d, J = 8.4 Hz, 1H), 4.61 (p, J = 6.3 Hz, 1H), 3.91 (dt, J = 14.4, 7.2 Hz, 1H), 3.75 (dd, J = 14.3, 7.3 Hz, 1H), 3.62 (dd, J =13.9, 6.9 Hz, 1H), 3.19 (p, J = 6.6 Hz, 1H), 2.59 (dd, J = 14.2, 7.2 Hz, 1H), 2.28 (s, 3H), 1.84 - 1.53 (m, 4H), 1.65 (d, J = 6.1 Hz, 6H), 1.28 (t, J = 7.3 Hz, 3H), 1.17 (d, J = 6.6 Hz, 3H), 1.12 (t, J = 7.5 Hz, 3H), 1.03 (s, 3H), 1.02 (d, J = 6.7 Hz, 3H), 0.93 (s, 3H).
Example 4
Ring Closing Metathesis of diallyi malonate
Figure imgf000089_0001
The data charted in Fig. 1 shows the results of Ring-Closing Metathesis of diethyl 2,2- diallylmalonate. The compounds AS9pl, AS28b7 and AS33M obtained in Examples 1, 2 and 3 were employed as catalysts.
Conditions were kept constant and the same for all catalysts: A 0.1M solution of the malonate in C6D6 with 0.02 equivalents catalyst and internal standard (anthracene) were loaded into a screw top NMR tube. The tube was loaded into a Varian NMR spectrometer and heated to temperature. Timepoints were taken using the Varian array function. It can be seen from Figure 1 that all three catalysts are active in Ring-Closing Metathesis.
Example 5
Ethenolysis of Methyl Oleate
Figure imgf000089_0002
Figure imgf000089_0003
, ps
Figure imgf000089_0004
Neutral alumina, Brockmann I, is activated by heating to 180 °C for 3 days under high vacuum. Methyl oleate is run through a plug of the neutral alumina and stored over fresh activated neutral alumina for 3 days. The reactions are run in a Fischer-porter flask with a dip-tube for taking aliquots under the conditions given in the equation above. Aliquots are diluted with hexane and cooled to -78 °C immediately and stored cold until analysis by gas chromatography. The compounds AS9pl, AS28b7 and AS33M obtained in Examples 1, 2 and 3 are employed as catalysts, showing ethenolysis activity as in the reaction equation given above.

Claims

What is claimed is:
1. An olefin metathesis catalyst comprising cyclic alkyl amino carbenes, represented by the structure of Formula (I):
Figure imgf000090_0001
Formula (I)
wherein:
M is Ru or Os;
L2 and L3 are independently neutral ligands;
m is 0, 1 or 2;
n is 0 or 1 ;
k is 0 or 1 ;
X1 and X2 are independently anionic ligands; generally, X1 and X2 are independently halogen, trifluoroacetate, per-fluorophenols, -NCO, -CN, -NCS, -N3; or X1 together with X2 can form a nitrate; typically, X1 and X2 are independently halogen, or -NCO;
R1 and R2 are independently selected from hydrogen, optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl; or any two or more of X1, X2, L2, L3, R1, and R2 are taken together to form one or more cyclic groups;
X is -CRlaR2a-;
a is 1 or 2;
Rla is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF , -S(0)xR25, - P(0)(0H)2, -0P(0)(0H)2, -SR27, or together with R2a forms an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R3 or together with R4 forms an optionally substituted polycyclic ring;
R2a is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, -S(0)xR25, - P(0)(0H)2, -0P(0)(0H)2, -SR27, or together with Rla forms a spiro monocyclic or spiro polycyclic C3-10 cycloalkyl or spiro heterocyclic ring, with the carbon atom to which they are attached, or together with R3 or together with R4 forms an optionally substituted polycyclic ring;
Y is -CRlbR2b-;
b is 0, 1 or 2;
R!b is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, -S(0)xR25, - P(0)(0H)2, -0P(0)(0H)2, -SR27, or together with R2b forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
R2b is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, halogen, optionally substituted C5-C24 aryl, optionally substituted C6-C24 aralkyl, optionally substituted C1-C20 heteroalkyl, - C(0)R21, - OR22, CN, - NR23R24, N02, -CF , -S(0)xR25, - P(0)(0H)2, -0P(0)(0H)2, -SR27, or together with Rlb forms a five-, six-, or ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;
R3 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, N02, - CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted Cs-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with Rla or together with R2a can form an optionally substituted polycyclic ring, or together with R3a can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl;
R3a is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, N02, - CF3, -S(0)XR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with Rla or together with R2a can form an optionally substituted polycyclic ring, or together with R3 can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl;
R4 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, - CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with Rla or together with R2a can form an optionally substituted polycyclic ring, or together with R4a can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl;
R4a is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, - CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with Rla or together with R2a can form an optionally substituted polycyclic ring, or together with R4 can form an optionally substituted spiro monocyclic or spiro polycyclic C3-10 cycloalkyl;
R5 is FT, optionally substituted Ci-24 alkyl, halogen- C(0)R21, - OR22, CN, - NR23R24, NO2, - CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R6 can form an optionally substituted polycyclic ring;
R6 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, -
CF3, - . S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R5 or together with R7 can form an optionally substituted polycyclic ring;
R7 is H, optionally substituted Ci-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, - CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R6 or together with R8 can form an optionally substituted polycyclic ring;
R8 is H, optionally substituted Ci-24 alkyl, halogen- C(0)R21, - OR22, CN, - NR23R24, NO2, - CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R7 or together with R9 can form an optionally substituted polycyclic ring;
R9 is H, optionally substituted C1-24 alkyl, halogen, - C(0)R21, - OR22, CN, - NR23R24, NO2, - CF3, -S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl, or together with R8 can form a polycyclic ring;
R21 is OH, OR26, NR23R24, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R22 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R23 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R24 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R25 is H, optionally substituted Ci-24 alkyl, OR22, - NR23R24, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R26 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
R27 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
x is 1 or 2; with the provisos
a. when a is 2, then the "X-X" bond can be saturated or unsaturated;
b. when a is 2, and the "X-X" bond is unsaturated, then R2a is nil; c. when b is 1 , then R3a and R4a are both nil;
d. when b is 2, then R3a and R4a are both nil;
e. when b is 2, the "Y-Y" bond can be saturated or unsaturated;
f. when b is 2, and the "Y-Y" bond is unsaturated, then R2b is nil.
2. An olefin metathesis catalyst of claim 1, wherein M is Ru.
3. An olefin metathesis catalyst of claim 1 or 2, wherein L2 and L3 are a phosphine, an NHC ligand, another cyclic alkyl amino carbene ligand or, is linked together with at least one of R1 or R2 or a cyclic group formed by R1 and R2.
4. An olefin metathesis catalyst of any of claims 1 to 3, wherein a is 1 or 2, b is 0, n is 0, k is 1, m is 0 or 1 or combinations thereof.
5. An olefin metathesis catalyst of any of claims 1 to 4, wherein X1 and X2 are the same or different and are independently selected from Cl, Br, I, trifluoroacetate.
6. An olefin metathesis catalyst of any of claims 1 to 5, wherein R1 and R2 are
independently selected from hydrogen, methyl, ethyl, ethenyl, 1,1-dimethylethenyl, or R1 and R2 are taken together to form one or more cyclic groups selected from indenyl, phenylindenyl or phenyl, and wherein optionally any two or more of R1 and R2, X1, X2, L2, L3 are forming a ring.
7. An olefin metathesis catalyst of any of claims 1 to 6, wherein R1 and R2 are taken
together to form one or more cyclic groups and said cyclic group is substituted with a group W- R15, wherein said group -W-R15 is L2, W is oxygen and R15 is alkyl.
8. An olefin metathesis catalyst of any of claims 1 to 7, wherein R5 and R9 are alkyl, in particular with one to five carbon atoms, preferably methyl, ethyl or isopropyl.
9. An olefin metathesis catalyst of any of claims 1 to 8, wherein R3 and R3a are selected from methyl, ethyl, isopropyl or R3 and R3a together are forming a cyclopentyl or cyclohexyl ring.
10. An olefin metathesis catalyst of any of claims 1 to 9, wherein R4 and R4a are selected from methyl, ethyl, isopropyl or R4 and R4a together are forming a cyclopentyl or cyclohexyl ring.
11. An olefin metathesis catalyst of any of claims 1 to 10, wherein X is CBh, and a is 1 or 2.
12. An olefin metathesis catalyst of any of claims 1 to 11, wherein R1 and R2 are taken together are forming a phenyl ring that is substituted up to three times with a group selected from Ci_24 alkyl, halogen, , - C(0)R21, - OR22, CN, - NR23R24, N02, -CF3, - S(0)xR25, -P(0)(0H)2, -0P(0)(0H)2, -SR27, and R21 is OH, OR26, NR23R24, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, R22, R23, R24 and R27 are, independently from each other, H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, R25 is H, optionally substituted Ci-24 alkyl, OR22, - NR23R24, optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, R26 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl.
13. An olefin metathesis catalyst of any of claims 1 to 12, wherein R15 is selected from H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu.
14. An olefin metathesis catalyst of any of claims 1 to 13, wherein R21 is OH, OR26, NR23R24, or optionally substituted Ci-6 alkyl; R22, R23, R24, R26 are H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu R25 is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, OR22, or - NR23R24.
15. An olefin metathesis catalyst of any of claims 1 to 13, wherein R6, R7 and R8 are,
independently from each other, are H, optionally substituted Ci-6 alkyl, halogen, optionally substituted phenyl.
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WO2022038121A1 (en) 2020-08-17 2022-02-24 Apeiron Synthesis S.A. Novel ruthenium complexes, methods of their preparation and application thereof in olefin cross metathesis
EP4180421A1 (en) * 2021-11-16 2023-05-17 Ecole Nationale Supérieure de Chimie de Rennes Iminium salts with a barralene ring, corresponding ruthenium complexes, and uses thereof
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