WO2014172885A1 - Catalyseurs à métal de transition du groupe 9 et procédé d'utilisation de ceux-ci - Google Patents

Catalyseurs à métal de transition du groupe 9 et procédé d'utilisation de ceux-ci Download PDF

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WO2014172885A1
WO2014172885A1 PCT/CN2013/074755 CN2013074755W WO2014172885A1 WO 2014172885 A1 WO2014172885 A1 WO 2014172885A1 CN 2013074755 W CN2013074755 W CN 2013074755W WO 2014172885 A1 WO2014172885 A1 WO 2014172885A1
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group
alkyl
catalyst
substituted
aryl
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PCT/CN2013/074755
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Francis Walter Cornelius Verpoort
Heriberto DIAZ VELAZQUEZ
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Guang Ming Innovation Company (Wuhan)
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Priority to CN201380077684.9A priority Critical patent/CN105531028B/zh
Priority to PCT/CN2013/074755 priority patent/WO2014172885A1/fr
Publication of WO2014172885A1 publication Critical patent/WO2014172885A1/fr

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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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
    • 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
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper

Definitions

  • This invention relates generally to organometallic catalysts suitable for the CLICK reaction, and reactions involving carbon dioxide as substrate. More particularly catalyst compounds suitable azide-alkyne cyclo-addition, their synthesis and processes for the use thereof. As well catalyst compounds suitable for conversion of carbon dioxide generating cyclic or poly carbonates and carboxylic acids.
  • the invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.
  • the reaction is not significantly affected by the steric and electronic properties of the groups attached to the azide and alkyne reactive centers.
  • azides carrying a primary, secondary, or tertiary group; electron-deficient or electron-rich group; and aliphatic, aromatic, or hetero-aromatic substituent usually react well with variously substituted terminal alkynes.
  • reaction is unaffected by water and by most organic and inorganic functional groups; thus, all but eliminating the need for protecting-group chemistry.
  • un-catalyzed thermal cycloaddition of azides to alkynes usually requires prolonged heating and results in mixtures of the 1 ,4- and 1 ,5-disubstituted regioisomers.
  • copper catalyzed Azide Alkyne Cyclization(AAC) produces only 1 ,4-disubstituted-1 ,2,3-triazoles at room temperature in excellent yields.
  • the rate of the metal-catalyzed process is approximately 107 times that of the un-catalyzed version, 5 making the reaction conveniently fast in the temperature range of 0 to 25 °C. Furthermore, ligand-accelerated-catalysis effects 18 are also significant, resulting in further increases in the reaction rate.
  • the 1 ,2,3-triazole unit that results from the reaction has several advantageous properties: (i) a high chemical stability (in general, being inert to severe hydrolytic, oxidizing, and reducing conditions, even at high temperature), (ii) a strong dipole moment (5.2-5.6 D), (iii) an aromatic character, and (iv) a good hydrogen-bond-accepting ability. 19,20 Thus, it can interact productively in several ways with biological molecules, and serve as a replacement for the amide linkage in some circumstances. A number of different copper(l) sources can be utilized in the reaction.
  • Copper(l) salts (CuCI, Cul, CuBr, CuOAc) and coordination complexes (such as [Cu(CH 3 CN) 4 ]PF 6 , 16 (EtO) 3 P « Cul, 21 [Cu Pha ⁇ Br 22 ' 23 ) can be used directly.
  • the latter have been particularly effective in organic solvents, in which cuprous salts have limited solubility.
  • Cu(l) is thermodynamically unstable and can be relatively easily oxidized to catalytically inactive Cu(ll).
  • the standard potential of the Cu2+/Cu+ couple is 159 mV, but can vary widely with the solvent and the ligand environment of the metal.
  • Cu(ll) itself, is an oxidant and can mediate the oxidative alkyne coupling reactions mentioned above, thereby impairing the efficiency of the cycloaddition and resulting in the formation of undesired byproducts. Therefore, when a copper(l) catalyst is used directly, whether by itself or in conjunction with amine ligands, exclusion of oxygen may be required to prevent these complications.
  • a sacrificial reducing agent for example ascorbate
  • a copper(ll) salt e.g. copper(ll) sulfate pentahydrate or copper(ll) acetate. 17
  • Catalytic amounts of Cu(l) can also be introduced in the reaction through com-proportionation of Cu(ll) and Cu(0), thus further simplifying the experimental procedure.
  • Copper nanoclusters which are easily obtained and are air-stable, 24 and copper/cuprous oxide nanoparticles 25 have also shown good catalytic activity, although this procedure requires longer reaction times.
  • TBTA ligand tris[(1-benzyl-1 H-1 ,2,3-triazol-4-yl)methyl]amine
  • the catalysts of this invention can also be applied to synthesize cyclic- and poly-carbonate products. Synthetic procedures which utilize C0 2 as a carbon feedstock are currently generating great interest within the scientific community 28 as these may offer viable alternative routes toward various organic structures that are currently derived from fossil fuel based resources 29 .
  • the catalysts of this invention can also be applied to synthesize carboxylic acids using C0 2 .
  • Carboxylic acids are one of the most important types of compounds in medicinal chemistry and also in fine-chemicals synthesis 35, 36 .
  • the direct carboxylation of carbon nucleophiles using C0 2 as the electrophile is the most attractive and straightforward method 35,36 .
  • the formation of a stable C— C bond is desired for C0 2 fixation and remains the most challenging aspect thus far.
  • this type of reaction is facilitated by the insertion of C0 2 into a metal-carbon bond 35"37 . Widespread use of these methods is limited by the synthesis organometallic reagents as precursors and the restricted substrate scope.
  • the present invention introduces the use of water-soluble complexes for the Azide Alkyne Cycloaddition preferably in aqueous media, without the need of external bases or extra ligands and using low catalyst loadings, in which the synthesis of triazoles using either internal or terminal alkynes, as well as acetylene gas with organic azides is aimed.
  • the present invention is not limited to organic azides, since it is possible to use /n-s/ft/generated HN 3 (from inorganic azides) for the synthesis of 4- and 4,5-substituted triazoles under aqueous conditions by using these catalysts. Furthermore, the efficiency of these catalysts is also proven by its excellent performance in peptidomimetic chemistry.
  • the present invention also relates to an easy applicable catalyst synthesis and the application in different click-processes.
  • the organometallic catalyst compound of the present invention can be prepared by contacting a Group 9metal precursor compound with atwo-electron donating ligand bearing two ionic groups or with a two-electron donating ligand bearing one ionic group.
  • M is a Group 9 transition metal
  • X is preferably an anionic ligand.
  • L 1 and L 2 represent identical or different ligands, preferably electron donors.
  • G 1 and G 2 represent an ionic group.
  • a " is an anion, preferable a non-coordinating
  • the invention provides novel organometallic compounds according to the above structure.
  • the invention provides a method for performing a catalytic cycloaddition reaction comprising contacting at least one alkyneand an azide compound with the "click' -catalyst of the invention.
  • a substituent encompasses a single substituent as well as two or more substituents, and the like.
  • substituted means that a hydrogen atom or an atom is replaced by a specified group or an atom, and the valence of the atom indicated is not exceeded and the substitution leads to a stable compound.
  • Figure 1 depicts the comparison of bis(NHC)-Cu catalysts for the click reaction between phenylacetylene and benzylazide.
  • alkyl refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms.
  • C i-C 6 -alkyl
  • cycloalkyl intends a cyclic alkyl group, typically having 3 to 8 carbon atoms.
  • 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. If not otherwise indicated, the term “alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl.
  • alkylene refers to a difunctional linear, branched, or cyclic alkyl group, where "alkyl” is as defined above.
  • alkenyl refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, and the like.
  • Preferred alkenyl groups herein contain 2 to about 12 carbon atoms.
  • cycloalkenyl intends a cyclic alkenyl group, preferably having 5 to 8 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. If not otherwise indicated, the term “alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl.
  • alkenylene refers to a difunctional linear, branched, or cyclic alkenyl group, where "alkenyl” is as defined above.
  • alkynyl refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms.
  • 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. Ifnot otherwise indicated, the term “alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl respectively.
  • alkoxy intends 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 refers 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 5 to 14 carbon atoms.
  • Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, 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 infra.
  • 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 5 to 14 carbon atoms.
  • aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxyphenoxy, 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.
  • Alkaryl groups include, but not limit to, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2, 7 -dimethylnaphthyl, 7 -cyclooctyl naphthyl, 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-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like.
  • alkaryloxy and aralkyloxy refer to substituents of the formula -OR wherein R is alkaryl or aralkyl, respectively, as just defined.
  • acyl refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, or -(CO)-aralkyl
  • acyloxy refers to substituents having the formula -0(CO)-alkyl, -0(CO)aryl, or -0(CO)-aralkyl, wherein "alkyl,” “aryl, and “aralkyl” are as defined above.
  • 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.
  • halo and halogen are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.
  • Hydrocarbyl refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like.
  • hydrocarbylene intends a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species.
  • Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups
  • heteroatom-containing hydrocarbyl and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom
  • substituted hydrocarbylene refers to hydrocarbylene substituted with one or more substituent groups
  • heteroatomcontaining hydrocarbylene and “heterohydrocarbylene” refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom.
  • hydrocarbyl and hydrocarbylene are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.
  • 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.
  • 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.
  • 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 alkoxyalkyl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like.
  • heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1 ,2,4-triazolyl, tetrazolyl, etc., and examples of heteroatom containing alicyclic groups are pyrrolidino, morpholino, piperazino, piperidino, etc.
  • 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: functional groups such as halo, hydroxyl, sulfhydryl, C 1 -C24 alkoxy, C 2 -C 2 4 alkenyloxy, C 2 -C 2 4 alkynyloxy, C 5 -C 24 aryloxy, C 6 -C 24 aralkyloxy, C 6 -C 24 alkaryloxy, acyl (including C 2 C 24 alkylcarbonyl (-CO-alkyl) and C 6 -C 24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C 2 C 2 alkylcarbonyloxy (-O-CO-alkyl) and C 6 -C 24 arylcarbonyloxy (-O-CO-aryl)), C 2 C 24 alkoxycarbonyl (-(CO)-O-alkyl), C 6 -C 2 aryloxycarbonyl (-(CO)-aryl), halocarbony
  • the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional 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 functional groups or additional hydrocarbyl moieties such as those specifically enumerated.
  • the present invention comprises the use of water-soluble group 9transition metal complexes for the AAC preferably in aqueous media, without the need of external bases or extra ligands and using low catalyst loadings, in which the synthesis of triazoles using either internal or terminal alkynes, as well as acetylene gas with organic azides is aimed.
  • the present invention is not limited to organic azides, since it is possible to use in-situ generated HN 3 (from inorganic azides) for the synthesis of 4- and 4,5-substituted triazoles under aqueous conditions by using these catalysts. Furthermore, the efficiency of these catalysts is also proven by its excellent performance in peptidomimetic chemistry.
  • this invention comprises an azide and an alkyne, in which the catalysts have either of the following structures (I) or (II)
  • X is an anionic ligand.
  • X is for example, hydrogen, halogen, pseudohalogen, straight-chain or branched C1-C30 alkyl, C 6 -C 24 aryl, CrC 20 alkoxy, C 6 -C 2 aryloxy, C 3 -C 20 alkyl diketonate, C 6 -C 24 aryl diketonate, Ci-C 2 o carboxylate, Ci-C 2 o alkylsulfonate, C6-C 24 aryl sulfonate, Ci-C 2 o alkyl thiol, C6-C 24 aryl thiol, Ci-C 2 o alkylsulfonyl or Ci-C 2 o alkylsulfinyl-radical.
  • X may further be substituted by one or more additional residues, for example by halogen, preferably fluorine, CrC 20 alkyl, Ci-C 20 -alkoxy or C 6 -C 24 aryl, where these groups may optionally be in turn be substituted by one or more substituents from the group comprising halogen, preferable fluorine, C 1 -C5 alkyl, C 1 -C5 alkoxy, and phenyl.
  • halogen preferably fluorine, CrC 20 alkyl, Ci-C 20 -alkoxy or C 6 -C 24 aryl, where these groups may optionally be in turn be substituted by one or more substituents from the group comprising halogen, preferable fluorine, C 1 -C5 alkyl, C 1 -C5 alkoxy, and phenyl.
  • X denote a halogen, in particular, fluorine, chlorine, bromine or iodine, benzoate, C 1 -C5 carboxylate, C 1 -C5 alkyl, phenoxy, C 1 -C5 alkoxy, C 1 -C5 alkyl thiol, C6-C24 arylthiol, C6-C 24 aryl or C 1 -C5 alkyl sulfonate.
  • halogen in particular, fluorine, chlorine, bromine or iodine
  • X is fluorine, chlorine, bromine or iodine, PhO (phenoxy), C 6 F 5 0 (pentafluorophenoxy).
  • G 1 and G 2 are identical or different functional groups, preferably represent ionic groups.
  • G is an ionic group or contains an ionic group
  • the ionic group can be cationic or anionic.
  • Preferable groups are e.g. quaternary ammonium, carboxylate, sulphonate (-SO 3 " ), -OSO 3 " , -PO 3 " , OPO 3 " .
  • the ionic group bears a counter ionto neutralize the charge, in case the ionic group is a cation the counter ion will be anionic, in case the ionic group is an anion the counter ionwill be cationic.
  • L represents an electron donor
  • L represents a N-Heterocyclic carbene ("NHC”), substituted NHC, or cyclic alkyl amino carbene (CAAC) or substituted CAAC.
  • NHC N-Heterocyclic carbene
  • CAAC cyclic alkyl amino carbene
  • R 1 - R 8 , R 5 , R 6 are identical or different and are hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF 3 , nitro, nitroso, cyano, thiocyano, isocyanates, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, ammonium, silyl, acyl, acyloxy or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbon
  • one or more of the radicals R 1 - R 8 , R 5 , R 6 independently of one another can be substituted by one or more substituents, preferably straight or branched C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 10 alkoxy or C 6 -C 2 4 aryl, where these aforementioned substituents may in turn be substituted by one or more radicals, preferably selected from the group comprising halogen, especially chlorine or bromine, C 1 -C5 alkyl, C 1 -C5 alkoxy and phenyl.
  • R 1 , R 2 , R 5 , R 5 , R 6 and R 6 are independently of one another denote hydrogen, C 6 -C 2 4-aryl, particularly preferably phenyl, straight or branched C1-C10 alkyl, particularly preferably propyl or butyl, or together with the inclusion of the carbon atoms to which they are attached form a cycloalkyi or aryl radical, where all the abovementioned radicals are optionally substituted may be substituted by one or more further radicals selected from the group comprising straight or branched Ci- C10 alkyl, C1-C10 alkoxy, C 6 -C 2 4 aryl, and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulf
  • the catalysts of the general formula (I) having one N-Heterocyclic carbene (NHC) as ligand L where the radicals R 3 , R 4 , R 7 and R 8 are identical or different and are straight or branched C C 0 alkyl, particularly preferably / ' -propyl or neopentyl, C 3 -C 10 cycloalkyi, preferably adamantyl, C6-C24 aryl, particularly preferably phenyl.
  • N-Heterocyclic carbene N-Heterocyclic carbene
  • the above-mentioned residues are substituted as the meanings of R 3 , R 4 , R 7 and R 8 by one or more further radicals selected from the group comprising straight or branched C1-C5 alkyl, especially methyl, C1-C5 alkoxy, aryl and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
  • one or more further radicals selected from the group comprising straight or branched C1-C5 alkyl, especially methyl, C1-C5 alkoxy, aryl and a functional group selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine imine,
  • R 3 , R 4 , R 7 and R 8 are aryl, in each case two directly adjacent radicals from the group of R 3 , R 4 , R 7 and R 8 , including the ring carbon atoms to which they are attached by a cyclic bridging group, generating one or more cyclic structures, including aromatic structures.
  • C1-C6 alkyl is, but not limited to, for example methyl, ethyl, n-propyl, /so-propyl, n-butyl, sec- butyl, feri-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, neo-pentyl, 1 -ethyl-propyl and n-hexyl.
  • C 3 -C 8 cycloalkyi includes, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • C 6 -C 2 4 aryl includes an aromatic radical having 6 to 24 skeletal carbon atoms.
  • Preferred mono-, bi-or tricyclic carbocyclic aromatic radicals have 6 to 10 skeletal carbon atoms, for example but not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl or anthracenyl.
  • radicals R 3 , R 4 , R 7 and R 8 can be identical or different and denote / ' -propyl, neopentyl, adamantyl, mesityl or 2,6-diisopropylphenyl.
  • N-Heterocyclic carbenes have the following structure (IVa) - (IVh).
  • one of the N groups bound to the carbene in Formulae (Ilia) or (1Mb) is replaced with another heteroatom, preferably S, O or P, preferably an S heteroatom.
  • Other useful N-heterocyclic carbenes include the compounds described in Hermann, W A. Chem. Eur. J 1996, 2, 772 and 1627; Enders, D. et al., Angew. Chem. Int. Ed. 1995, 34, 1021 ; Alder R. W., Angew. Chem. Int. Ed. 1996, 35, 1 121 ; and Bertrand, G. et al., Chem. Rev. 2000, 100, 39.
  • CAACs cyclic alkyl amino carbenes
  • ring A is a 4-, 5-, 6-, or 7-membered ring
  • Z is a linking group comprising from one to four linked vertex atoms selected from the group comprising C, O, N, B, Al, P, S and Si with available valences optionally occupied by hydrogen, oxo or R- substituents
  • R is independently selected from the group comprising Ci to C 12 hydrocarbyl groups, substituted Ci to C 12 hydrocarbyl groups, and halides
  • each R 9 is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl,
  • CAACs include the compounds described in U.S. 7,312,331 and Bertrand et al, Angew. Chem. Int. Ed. 2005, 44, 7236-7239.
  • L 1 and L 2 represent two electron donor ligands.
  • L 1 and L 2 are the same or different and represent a N-Heterocyclic carbene ("NHC”), substituted NHC, or cyclic alkyl amino carbene (CAAC) or substituted CAAC.
  • NHS N-Heterocyclic carbene
  • CAAC cyclic alkyl amino carbene
  • R - R , R and R have the same meanings as in the general formula (I).
  • a " is an anion, preferable a weak-coordinating anion or a non-coordinating anion.
  • suitable weak-coordinating and non-coordinating anions include, but are not limited to, [BF 4 ] ⁇ , [PF 6 ] ⁇ , and [CIO 4 ] " , Trifluoromethanesulfonate, B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 ] ⁇ , tetrakis(pentafluorophenyl)borate, carborane anion.
  • the invention describes the synthesis of catalysts by using different metal(l) sources depending of the type of catalysts being synthesized.
  • Type (I) catalysts based on Au(l) but not limited to can use the salts AuCI, AuBr, Aul.
  • Type (II) catalysts require the use of the complexes such as but not limited to [Cu(CH 3 CN) 4 ]PF 6 , [Cu(CH 3 CN) 4 ]BF 4 , [Au(CH 3 CN) 4 ]PF 6 , [Au(CH 3 CN) 4 ]BF 4
  • the catalyst compounds described in this invention may be synthesized by any methods known to those skilled in the art.
  • R 10 - R 12 are identical or different and are hydrogen, or represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, substituted alkenyl, heteroalkenyl, heteroatom-containing alkynyl, alkenylene, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkaryl, aralkyl, alkaryloxy, aralkyloxy, alkoxycarbonyl, alkylammonium, alkylamino-, alkylthio-, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylsilyl or alkoxysilyl, where these radicals may each optionally all be substituted by one or more aforementioned groups defined for
  • one or more of the radicals R 10 - R 12 independently of one another can be substituted by one or more substituents, preferably straight or branched C-
  • R 11 and R 12 independently of one another can be a metal, preferable a transition metal.
  • multimetal entities can be prepared. Using this concept "a la carte” multimetal 1 ,2,3-triazole derivatives can be prepared.
  • R 12 H .
  • R 11 and R 12 are different from hydrogen.
  • R 11 and R 12 are H.
  • R 10 H
  • Reactants containing the alkyne functionality can be aliphatic or aromatic holding various electronic and steric properties.
  • Both terminal and internal alkynes can be used in the practice of this invention.
  • Both types of alkyne can contain functional groups. Examples of these functional groups include but are not limited to: carbon-carbon double bonds, ether groups, ester groups, ketyl groups, hydroxyl groups, chlorine groups, fluorine groups, trihydrocarbylsilyl groups, nitrogen atoms (e.g., as amino groups) and the like.
  • terminal alkynes typically have three to about twenty carbon atoms, and preferably about five to about twenty carbon atoms.
  • the invention is also applicable to molecules holding multiple terminal alkyne groups in each endof the same molecule (e.g. but not limited to dendrimeric compounds) or holding multiple internal alkyne groups.
  • Reactants containing the azide functionality include, but are not limited to: alkyl azides, ether azides, aryl azides and aralkyl azides.
  • One or more functional groups can be included, e.g. cyano groups, nitro groups, amino groups, alkyl groups, halide groups, ester groups, ether groups, carboxylic groups, alkylsilyl groups, hydroxyl groups, alkenyl groups may be present in an aryl azide, in an aralkyl azide or in an alkyl azide.
  • the alkyl portion of the alkyl azides can be branched, straight chain or cyclic group. Typically the alkyl azides have one to about twenty carbon atoms. In case of alkyl azides lower than 4 carbon atoms, a reaction procedure is followed, in which alkylazidesare generated/n-s/ft/ during the catalysis.
  • the invention is also applicable to molecules holding multiple azide groups in each end of the same molecule, in which the final multi-azide is stable enough to perform the reactions under normal ambient conditions.
  • the inorganic azide HN 3 this is generated in-situ by reaction of NaN 3 trimethylsilylazide or CaN 3 with a hydrogen source,
  • peptides containing 2 to 20 aminoacid residues in which there is at least one azide group and/or one terminal alkyne group include, but are not limited to peptides containing 2 to 20 aminoacid residues in which there is at least one azide group and/or one terminal alkyne group.
  • the peptides susceptible for chemical transformation by the catalysts of this invention may hold every aminoacid present in the proteins, including those susceptible to complexation and/or sensitive to oxidation.
  • the catalysts for the chemical ligation of peptides can be used with chemically protected peptides or unprotected peptides preferably in an aqueous media.
  • Solvent is not usually necessary in the processes of this invention, in which a neat process will be followed.
  • non-neat processes generally it is recommended and preferred to conduct the processes of this invention in water, alcohol-water mixtures, DMSO-water mixtures, DMF-water mixtures or solvents different than water, preferably polar solvents like DMSO, acetone, acetonitrile, DMF or lower alcohols like methanol, ethanol or propanol.
  • concentrations of the organic azide and the alkyne are each, independently, typically about 1 molar or higher, however, lower concentrations can be employed.
  • concentrations of the organic azide and the alkyne are each, independently, typically about 1 molar or higher, however, lower concentrations can be employed.
  • one mole of organic azide and one mole of alkyne are consumed for each mole of 1 ,2,3-triazole produced.
  • the amounts of organic azide and alkyne are preferably such that the alkyne is in slight excess relative to the organic azide.
  • acetylene gas one atmosphere of acetylene gas is used by bubbling it into the reaction vessel.
  • the inorganic azide HN 3 preferable, but not limited to, 1.5 mol HN 3 per mol of alkyne is used.
  • Catalytic amounts of the catalysts of this invention are used. More particularly, the amount of catalyst is usually in the range of about 0.001 mol% to about 10mol% relative to the terminal alkyne. Preferably, about 0.5mol% to about 5mol% of the catalyst relative to the organic azide is employed. When the alkyne is a terminal alkyne, more preferred amounts of the catalyst are in the range of about 0.1 to 2mol% relative to the organic azide. When the alkyne is an internal alkyne, more preferred amounts of the catalyst are in the range of 5 to 10mol% relative to the organic azide. When peptide synthesis is conducted, it is preferred to use 5 equivalents of catalyst relative to the number of molecules of peptide.
  • Temperatures during the processes of the invention generally range from 0°C to 140°C and preferably from about room temperature to 1 10°C.
  • the preferred working temperature is about room temperature, depending on the melting point of the alkyne, in which case the temperature will subject to that value.
  • temperatures from 50°C to about 80°C are preferred.
  • the temperature range goes from 100 to 1 10°C.
  • the working temperature is preferably room temperature.
  • the processes of this invention comprises a wide range of reaction times, depending on the reaction conditions and the nature of the reactants involved in the catalysis, the reaction times arein the order of minutes (5 to 20minut.es) to hours (2 to 18hours) when acetylene gas, terminal alkynes with organic and/or inorganic azides are used. Internal alkynes react more slowly than do terminal alkynes and/or acetylene; therefore the reaction times are longer. Addition of a higher catalyst loading and/or increasing the reaction temperature may shorten the reaction time. When using acetylene gas and/or terminal alkynes, water may be used to shorten the reaction time. When the 1 ,2,3-triazole products are oils or low melting point solidslonger reaction times are required. Peptide synthesis requires longer reaction times, which are in the range of 12 to 48h, and 18h is the preferable reaction time.
  • the 1 ,2,3-triazole products are generally solids, which can be isolated by standard techniques such as precipitation or centrifugation and decantation, depending of the solvent used, it may be necessary to extract with an organic solvent and purify by column chromatography. For oily products, solvent extraction and/or column chromatography are the typical purification methods. Peptides are mainly purified by HPLC techniques.
  • an organic azide (1 .0 mmol), an alkyne (1 .05mmol) and catalyst Bis[1-(4-sodiumsulfonatebutyl)-3-(2,4,6-trimethylphenyl)-4,5-dihydroimidazolyl-3-ylidine] copper (I) hexafluorophosphate (IMDS 2 -Cu) (0.5mol% unless specified), are added.
  • IMDS 2 -Cu 0.5mol% unless specified
  • the invention comprises reactions in aqueous media for which the stability of the azide is too low to be isolated and used as pure.
  • a procedure in which the azide was formed in-situ from alkyl and/or aryl halide is used.
  • Water and room temperature are the preferred conditions, however, mixtures of water and a polar organic solvent like water/Dimethylsulfoxide, water/acetonitrile, water/alcohol (preferably lower alkyl alcohols: methanol, ethanol, isopropanol or fert-butanol) are also possible to use.
  • the reactions may be carried out at a temperature range of 20-75°C.
  • the order ofpreference for halide substituents in the alkyl or aryl group are: l>Br>CI.
  • alkyl halide (1 mmol) and NaN 3 (1 .1 mmol) and 1 ml_ of water (unless otherwise noted) were added.
  • the reaction was allowed to proceed at room temperature (unless otherwise noted) and monitored by 1 H NMR analysis of aliquots. After total consumption of the starting azide, the solid product was collected by filtration and washed with water and pentane. In case of oily products, these were extracted with dichloromethane and washed with aqueous NH 4 CI. Examples of the triazoles synthesized by this procedure are given in table 4along with the yields and reaction times.
  • the invention comprises the synthesis of triazoles in which no substituent is present in the 4,5-positions, by using CaC 2 and acetylene gas as the alkyne source.
  • CaC 2 as the source of acetylene:
  • the reaction was stirred at room temperature and monitored by TLC. After the reaction was completed, the mixture was acidified at pH ⁇ 5 with HCI 0.1 N and the organic material was washed with brine and extracted with diethyl ether. In case the product is not pure enough, column chromatography may be needed.
  • the synthesis of the peptides was followed under standard conditions using microscale techniques. It is possible the use of pH buffers to the solutions of peptides in order to maintain its properties, however highly acidic media may decrease the activity of the catalyst. Co-solvents are also susceptible to be used when the solubility of the peptides is a major issue. For that case MeOH, DMSO, NMP and/or HFIP (Hexafluoroisopropanol)may be used. For the case of poor soluble peptides, the first option for co-solvent should be HFIP. There is no preference on the order of addition for the substrates and/or catalyst. The catalysis is carried out preferably under ambient conditions of temperature and with long reaction times.
  • Neat DMAP 10 120 92 General Procedure for Carboxylation of the Terminal Alkynesis exemplified using phenylacetylene, scheme 6.
  • the catalysts of this invention can also be immobilized in an efficient and straightforward manner, scheme 7.
  • the catalysts can easily be recovered and reused for the next run as exemplified with
  • Immobilization of the catalysts of this invention is not limited to resins bearing ionic groups.
  • the catalysts of this invention can be immobilized on any support (organic, inorganic, ionic liquids, etc.) bearing ionic groups, e.g. inorganic supports which have been modified so that they possess ionic groups, organic support bearing ionic groups, metal organic frameworks with ionic groups and so on. Some examples, but not intended to limit are giving above mentioned.
  • 29.111ustrative examples of new conversions include: (a) C. Das Neves Gomes, O. Jacquet, C. V Amsterdam, P. Thuery, M. Ephritikhine, T. Cantat, Angew. Chem., Int. Ed. 2012, 51 , 187. (b) O. Jacquet, C. Das Neves Gomes, M. Ephritikhine, T. Cantat, J. Am. Chem. Soc. 2012, 134, 2934. (c) D. Yu, Y. Zhang, Proc. Natl. Acad. Sci. U.S.A. 2010, 107, 20184.

Abstract

La présente invention concerne des catalyseurs à métal de transition de groupe 9 et un procédé d'utilisation des catalyseurs dans la cyclo-addition d'alcyne-azide (réaction de Click), dans une réaction utilisant CO2 en tant que matière première carbonée pour réagir avec des époxydes pour produire des produits cycliques ou de polycarbonate et dans des réactions utilisant CO2 en tant que matière première carbonée pour réagir avec des alcynes terminaux pour produire des acides carboxyliques. Les composés catalyseurs de l'invention sont représentés par la formule (I) : et par la formule (II) : où M est un métal du groupe 9 ; X est un ligand anionique ; L est un ligand donneur de deux électrons comportant deux groupes ioniques (G) où M est un métal du groupe 9 ; L1 et L2 sont des ligands donneurs de deux électrons comportant chacun un groupe ionique (G) et A- est un anion. La présente invention concerne en outre une synthèse de catalyseur aisément applicable et l'application dans différents procédés de Click, différentes réactions impliquant CO2 et leurs différents domaines d'application. L'invention présente une utilité dans les domaines de la catalyse, de la synthèse organique, de la chimie des polymères, et de la chimie industrielle et des produits chimiques fins.
PCT/CN2013/074755 2013-04-26 2013-04-26 Catalyseurs à métal de transition du groupe 9 et procédé d'utilisation de ceux-ci WO2014172885A1 (fr)

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CN113559924A (zh) * 2021-07-28 2021-10-29 绍兴七轩新材料科技有限公司 一种离子液体催化剂及其制备方法和应用
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