GB2447068A - Catalytic olefin metathesis reaction method - Google Patents

Catalytic olefin metathesis reaction method Download PDF

Info

Publication number
GB2447068A
GB2447068A GB0703509A GB0703509A GB2447068A GB 2447068 A GB2447068 A GB 2447068A GB 0703509 A GB0703509 A GB 0703509A GB 0703509 A GB0703509 A GB 0703509A GB 2447068 A GB2447068 A GB 2447068A
Authority
GB
United Kingdom
Prior art keywords
catalyst system
groups
group
reactions
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB0703509A
Other versions
GB0703509D0 (en
Inventor
Michael Green
Duncan Frank Wass
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Bristol
Original Assignee
University of Bristol
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Bristol filed Critical University of Bristol
Priority to GB0703509A priority Critical patent/GB2447068A/en
Publication of GB0703509D0 publication Critical patent/GB0703509D0/en
Priority to PCT/GB2008/000619 priority patent/WO2008102157A1/en
Publication of GB2447068A publication Critical patent/GB2447068A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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)
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/18—Preparation of halogenated hydrocarbons by replacement by halogens of oxygen atoms of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • 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
    • C07C6/06—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond at a cyclic 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
    • C07C67/343—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 by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • 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
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • 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
    • 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
    • B01J2531/824—Palladium
    • 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
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

A method for performing an olefin metathesis or cross-coupling reaction is characterised by the catalyst system comprising: [a] a source of a d-block metal, such as Group VIII metal, iron, cobalt, copper, ruthenium, rhodium, nickel, palladium or platinum [b] optionally a promoter, an activator and/or a base, and [c] a source of a 3-membered carbocyclic ligand. Also disclosed is catalysing olefin metathesis or cross-coupling reactions, comprising the catalyst system and a method of producing the catalyst system wherein [b] optionally a promoter, an activator and/or a base is a further reagent.

Description

CATALYTIC METHOD
The present invention relates to methods fpr performing olefin metathesis or cross-coupling reactions in the presence of a catalyst system, catalyst systems for use in the methods, processes for preparation of the catalyst systems and uses of the catalyst systems in the methods.
Complexes of transition metals have found widespread use as homogeneous catalysts (Applied Homogeneous Catalysis with Organometallic Compounds, Cornils, B.; Herrmann, W.A. (Eds), VCH Weinheim, 1996, 258). They are particularly useful for catalytic reactions involving the formation of carbon-carbon or carbon-heteroatom (for example, H, N, 0, P) bonds, two important classes of reaction being so-called cross-coupling' reactions (Metal Catalyzed Cross-Coupllng Reactions, 2 ed, de Meijere and Diederich (eds), Wiley-VCH, 2004) and metathesis' reactions (also known as olefin metathesis reactions) (Handbook of Metathesis, Grubbs (ed) Wiley-VCH, 2003).
A crucial consideration in these applications is the supporting ligands around the transftion metal centre, modification of which can lead to industrially useful benefits such as improved stability, selectivity and activity.
A number of such supporting ligands have been disclosed, often based on N-or P-donor sets. More recently, ligands based on cyclic hetercatom-stabilised C-donors have also been described, such ligands often being called N-heterocyclic carbenes (W A. Herrmann, C KOcher, Angewandte Chemie International Edition, 1997, 36, 2162-2187) and, even more recently, carbocyclic (i.e. no heteroatom) carbene ligands based on 7-membered rings have been disclosed (W.A. Herrmann et al, Angewandte Chemie International Edition, 2006, 45, 3859-3862).
Metal complexes supported by 3-membered carbocyclic ring ligands are known. A particular palladium complex with a cyclopropene ligand has been shown to catalyse an isomerisation reaction as disclosed in EP-A- 0118801 and Yoshida et al Tetrahedron 44, (1988) p55.
Other complexes based on cyclopropene have also been disclosed in Yoshida etal: Chemist,yLetters, 1978, 241 and 1341; J. Phys. Org. Chem., 1988, 332; Ofele, Angewante C/iemie. mt. Ed. 1968, 7, 950 (Cr); Schubert et al; J Am. Chem. Soc., 1991, 113, 2228 and Organometallics, 1988, 7, 784 (Mn).
However, use of these complexes as catalysts for reactions involving the formation of carbon-carbon or carbon-heteroatom bonds has not been disclosed.
We have found that, surprisingly, metal complexes with a 3-membered carbocyclic ring ligand are very efficient catalysts for such reactions and, moreover, show improved catalytic activity compared to other systems The present invention accordingly provides a method for performing an olefin metathesis or a cross-coupling reaction, characterised in that the method is performed in the presence of a catalyst system comprising, a) a source of a d-block metal, b) optionally a promoter, an activator and/or a base, and c) a source of a 3-membered carbocyclic ligand.
The d-block metal is preferably a Group VIII metal (referring to Chemical Abstracts Service group notation, 1986; Group VIII metals correspond to IUPAC recommended notation for Groups 8, 9 and 10 of the Periodic Table: the Fe, Co and Ni groups) or Cu, more preferably a Group VIII metal, and most preferably Ru, Rh, Ni, Pd or Pt. Preferably, the 3-membered carbocyclic ligand comprises a group of formula wherein (i) R1 and R2 are independently selected from hydrocarbyl or heterohydrocarbyl groups, or (ii) R and R2, together with the carbons to which they are attached, form a five, six, seven or eight membered ring.
The broken line in the formula of the carbocyclic ligand indicates the bond to the d-block metal.
Suitable hydrocarbyi groups are alkyl, for example methyl, ethyl, n-propyl, isopropyl, t-butyl, adamantyl; aryl or substituted aryl, for example phenyl, ortho-tolyl, meta-tolyl, para-tolyl, ethylphenyl, isopropylphenyl, t- butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, naphthyl, benzyl, alkenyl or alkynl groups. Suitable heterohydrocarbyl groups may have one or more heteroatorns and this may be attached directly to the 3-membered ring or at any other substituent position on the group. Suitable examples where the heteroatom is attached directly to the 3-membered nng are: -Z(R3)ITlwhereZisSiandrnis3,ZisNandmls2,zispandmjs2z is 0 and m is 1, or Z is S and m is 1; the groups R are the same or different hydrocarbyl groups as defined above.
Suitable examples where the heteroatom(s) are in other positions are: CF3, CF2CF3, CH2OMe, CH2NMe2, CH2CH2NH2, CH2CH2N(R52, CH2CH2P(R1)2, CH2CH2CH2F(R)2, fluorophenyl, perfluorophenyl, chiorophenyl, bromophenyl, C6H4(CF3), C6H3(CF3)2, C6H4(OMe), C6H3(OMe)2, C6H4(N(R')2), C6H4(P(R1)2), where R' is as defined above.
For some values of Rt and R2, these groups may themselves act as supporting ligands to the metal, for example when R' is CH2CH2P(R')2 the P-atom of this group may donate to the metal as a phosphine donor ligand. In this alternative, R1 andlor P2 are such that the 3-membered carbocyclic ligand is a multidentate ligand P and R', together with the carbons of the 3-membered ring to which they are attached, may form a five, six, seven or eight membered ring so that the ligand has a bicyclic structure.
The catalyst system may be formed in situ during the reaction or the catalyst system may be pre-formed.
If the catalysts system is pre-formed, the catalyst system may, preferably, comprise a compound of formula M ( L) wherein M is a d-block metal, n is 0 to 5 and the L groups, which may be the same or different, are ligands.
The L groups may be the same or different and are either additional ligands needed to stabilise the overall complex, for example, chloride, bromide, iodide, hydride, alkoxide, amide, acetate, acetylacetonate, amine, ether, water, phosphines such as triphenylphosphine or triphenoxyphosphine, pyridine, alkenes, alkynes, N-heterocyclic carbenes, etc; or reactive ligands that can be the active site of the catalysts, for example alkyl, aryl, carbene, alkylidene. Some of the L groups described as stabilising groups can also be reactive ligands in some circumstances, for example amide and hydride. L may also be a substrate molecule for the catalytic reaction being performed.
L may be a 3-membered carbocyclic ring ligand as defined above, giving an overall structure of: in the case where one L group is an additional 3-membered carbocyclic ring.
The value of n will vary depending on the nature of L and the required valericy of M but will generaily be between 0 and 5.
The olefin metathesis reaction may be selected from cross-metathesis, ring closing metathesis, enyne metathesis, ring opening metathesis, ring opening metathesis polymensation, acyclic diene metathesis or alkyne metathesis.
The cross-coupling reaction may be selected from 1) Cross-coupling reactions with organoboron compounds, for example Suzuki coupling, 2) Cross-coupling reactions with organotin compounds for example Stille coupling, 3) Cross-coupling reactions with organozinc compounds, 4) Cross-coupling reactions with organomagnesium compounds, 5) Crosscoupling reactions with other organometallic compounds, for example Negishi coupling, 6) Cross-coupling reacations with allylic compounds, 7) Cross-coupling reactions with conjugated diene compounds, 8) Carbometallation reactions, 9) Cross-coupling reactions with alkyne compounds, for example Sonogashira reaction, 10) Cross-coupling reactions with olefinic compounds, for example Heck reaction, 11) Cross-coupling reactions involving a cyclometallation step, 12) Cross-coupling reactions for the formation of carbon-heteroatom bonds (e.g. C-N, C-O), for example Buchwald-Hartwig reactions The detairs of such reactions are wefl-known to the skilled person as described in, for example, "Metal Catalysed Cross-coupling Reactions" 2 edition, edited by de Meijere and Diederich, Wiley-VCH 2004.
Catalytic reactions may be carried out on a wide variety of substrates including those that have been previously disclosed for cross coupling or metathesis catalysis and at temperatures between -100 C and 250 C, preferably between 0 C and 200 C. Reactions are typically carried out in a solvent diluent, although the substrates or reaction products themselves may also be used as solvents. The solvent diluent of choice will depend on the solubility characteristics of the specific catalysts and substrates used and a wide variety of suitable solvents are suitable, including hydrocarbons (e.g. (-) alkanes, benzene, toluene, xylene) and polar solvents (e.g. ethers, halocarbons, acetone, DMA, DMF, DMSO, MeCN etc.). Alternatively, the catalyst may be in the solid phase by heterogenisation on a suitable carrier such as a polymer, silica, carbon, alumina, etc For cross coupling catalysis, it is usually required to add a catalyst promoter, in excess, stoichiometric or sub-stoichiometric amounts to the substrates used. This promoter is usually a suitable base, such as an amine, amide, alkoxides, hydroxide, carbonate, phosphate or similar. Other possible promoters include halide ions. For metathesis catalysis, a promoter is usually not required, although in some specific cases one may be required to generate an active system.
In a second aspect, the present invention provides a catalyst system for catalysing olefin metathesis or cross-coupling reactions, the catalyst system comprising, a) a source of a d-block metal, b) optionally a promoter, an activator and/or a base, and c) a source of a 3-membered carbocyclic ligand Optional and/or preferred features of the catalyst system are generally as described above in relation to the first aspect of the invention.
Catalyst systems may be either pre-formed or formed in situ by mixing the component parts of the catalyst. Even in cases where a pre-formed catalyst system in the form of a discrete metal-ligand complex is used, this will often undergo further reaction during a catalytic run, resulting in a new complex in which the groups L have been removed, replaced or transformed into new L groups. Pre-formed catalyst systems may be made by those p skilled in the art by reaction of a transition metal source, a source of a 3 membered carbocyclic ligand and, optionally, a further reagent such as a base (for example: amines, amides, alkoxides, hydroxides, carbonates, BuLi or similar reagents), an acid, a reducing agent, an oxidising agent, or further group as defined as L above (or a source of a further group as defined as L).
Thus, in a third aspect, the present invention provides a method for producing a catalyst system for catalysing olefin metathesis or cross-coupling reactions, the method comprising combining a) a source of a d-block metal, b) optionally, a further reagent, c) a source of a 3-membered carbocyclic ligand.
Suitable sources of a transition metal are the metal itself, the metal dispersed on a suitable carrier material (for example silica or carbon) or a metal complex of formula ML1, where M and L are as defined above, and the value of m will vary depending on the nature of L and the required valency of M but will generally be between 1 and 6.
Suitable sources of a 3-membered carbocyclic ligand include the free carbene ligand: Such ligands are often unstable in their free form, and another suitable 3-rnembered carbocyclic ligand source is where the ligand has been stabilized by co-ordination to a Lewis acid fragment, as illustrated: :z where Z is a suitable Lewis acid, for example a main group Lewis acid such as a borane (eg. BH3, BCI3, BL3 and the like), appropriate group 13 compounds (e.g. AId3), appropriate group 14 compounds, (e.g. stannanes, SnCl2, SnCI4 and the like), appropriate group 15 compounds (e.g. SbF), or a further transition metal compound MLrn, as defined above.
S
Other suitable sources of a 3-membered carbocyclic ligand are substituted 3,3'-cyclopropene compounds as illustrated: where the X groups may be the same or different and may be a halide (F, Cl, Br, I, etc), pseudo-halide (e.g. N3, CN, NCO, OCN, etc.) or weakly-coordinating anion (eg. BF4, PF6, dO4, AsF6, Aid4, B(C6F5)4, etc), H, a main group metal or main group metal fragment (eg. Li, Na, K, MgCl) or transition metal fragment MLm as defined above.
The reagents may be combined in order to synthesise a pre-formed catalyst in a number of ways; for example: oxidative addition reaction of a low oxidation state metal source (eg. Pd metal, [Pd(PPh3)4, {RhCl(PPh3)3], [Ni(CO)4], etc) with a 3,3-dihalocyclopropene compound or analogous pseudo-halide or weakly-coordinating anion compound; reaction of a metal source with the free carbene; reaction of a metal source with 3,3'- dihalocyclopropene compound or analogous pseudo-halide or weakly-coordinating anion compound in the presence of a suitable reducing agent; reaction of a metal source with the free carbene; reaction of a metal source with the Lewis acid-protected carbene; reaction of a metal source with 3- halocyclopropene compound or analogous pseudo-halide or weakly-coordinating anion compound in the presence of a suitable base.
Subsequent modification of the complex to make other preformed catalysts with different L groups can be achieved by standard methods of ligand substitution, addition and/or removal.
Catalysts may also be formed in situ during a catalytic reaction, by addition of the various components as described above either in the presence or absence of the substrates to be converted during catalysis without isolating a discrete metal-ligand complex, although it is likely that similar complexes to those made using a the pre-formed method with be generated.
In this specification, for clarity, the bonding between the 3-membered carbocyclic ligand and the d block metal has been illustrated as This is only one of a number of resonance forms for this fragment having the same overall formula that could reasonably be drawn by those skilled in the art, and the description is not limited to this specific representation. The resonance form giving most accurate representation of this fragment is likely to vary between specific compounds and will depend on the other groups bonding to the 3-membered carbocycle.
In this specification, unless otherwise specified, "hydrocarbyl" refers to an optionally substituted hydrocarbon group and includes alkyl, alkenyl, alkynyl, 5-or 6-membered rings (that may be alicyclic or aryl and includes monocyclic, bicyclic or polycyclic fused ring systems), preferably C to C32, more preferably C to C24, most preferably C to C18 "Heterohydrocarbyl" refers to a group as defined above for hydrocarbyl but containing one or more heteroatoms preferably selected from Si, F, N, 0, S and F. Alkyl is preferably C1 to C6, more preferably straight chain C to C6 in particular methyl, ethyl, n-propyl or n-butyl The invention is illustrated by the Figure which is a single crystal X-ray diffraction structure of the compound described in Example 2.
The invention is further illustrated by the following Examples in which all procedures were carried out under an inert (N2) atmosphere using standard Schlertk line techniques or in an inert atmosphere (Ar) glovebox.
Chemicals were obtained from Sigma Aldrich and used without further purification unless otherwise stated.
Example 1. Synthesis of 1,2-diphenyl-3,3-dichlorocyclopropene I Diphenylcyclopropenone (1.00 g, 4.85 mmol) was heated at 40 C for 2 h in 2 ml of thionyl chloride The volatiles were removed in vacua to give a beige powder. The solid was dissolved in 6 ml of cyclohexane with heating and placed in a freezer overnight to give I.2-diphenyl-3,3-dichlorocyclopropene as pale yellow crystals in 59 % yield (0.75 g, 2 88 mmol).
Example 2. Synthesis of palladium complex 2 /C Ph3P CI 1,2-diphenyl-3,3-dichlorocyclopropene (47 mg, 0.18 mmol) and tctrokis(triphenylphosphne)pallad;um(0) (208 rig, 0.18 mmoi) were weighed into a Schlenk flask. 10 ml of toluene was added to give a yellow solution and a colourless precipitate immediately The mixture was stirred overnight The precipitate was collected by filtration and dried in vacua to give the illustrated compound 2 as a white solid in 50% yield. The product 2 can be recrystallised from CHCI3.
Charabteristic data: 31P{1H} NMR (121 MHz, CDCI3): O = 27.6, 1H NMR (400 MHz, CDCI3): 6 = 8.03 (m, 4H), 7.64 (m, 8H), 7.53 (m, 4H), 7.25 (m, 3H), 7.15 (it, 6H).
A single crystal X-ray diffraction structure of this compound was obtained and is shown in the Figure with significant bond lengths and angles in Table 1. In the Figure, hydrogen atoms are omitted for clarity. 1]
Table 1. Bond lengths (A) and angles ( ) Pdi-P1 2243 -.____ Pdi-Cll 2.362 Pdi-CI2 2.345 _______ 1.938 - C1-C2 -1.390 ____- C1-C3________ 1.387 - 2-C3 _____ 1.363 ____ LC2C1C3 59 ______ LIcic2c3 61 _____ f1Pd1C1______ 92 ____ Cli PdlCl2 ___ 93 Catalytic Experiments (see Table 2):
Examples 3-11
The same basic method was adopted for all of these examples for the illustrated reaction.
r,BuO RX _.? nBuO' R A Schlenk flask was charged with base as indicated in Table 2 (3.0 mmol), the aryl halide as indicated in Table 2 (2.0 mmol) and the internal standard diethylene glycol di-n-butyl ether (100mg). Then n-butyl acrylate (3 mmol) and degassed N,N- dimethylacetamide (DMA) (2 ml) were added and the reaction heated to 145 C. When the reaction had reached temperature, the required amount of catalyst 2 was added and the reaction stirred for the required run time. At the end of the reaction, the reaction mixture was allowed to cool, washed with dilute HCI (aq), extracted with dichioromethane and the organic phase dried over MgSO4. Conversion and yield was determined by GC relative to the internal standard. lfl 14.
Examples 12-16
Ph-B(OH)2 + R 2 Essentially the same method was used as described above, only n-butyl acrylate was replaced with phenylboronic acid, DMA was replaced with xylene and the reaction temperature was 130 00
Table 2:
Example R X Base Mol % Pd Conversion TON 3 C(O)Me Br NaOAc 0.0k 1 00 10 000 4 C(O)Me Hr NaOAc 10" 99 99 000 C(O)Me Br NaOAc I 0 94 940 000 6 H Br NaOAc 1 0 80 80 000 7 OMe Br NaOAe 10" 54 54000 8 C(O)Me CI NaOAc 1 98 98 9 C(O)Me Cl K2C01 1 100 100 C(O)Me (1 KC04 I 0 3 I 310 000 11 H Br K3C03 1 96 96 12 II Br Cs'C01 1 99 99 13 OMe Br KCO 1 97 97 14 C(O)Me Br K2CO 1 100 tOO C(O)Me Cl I i4 14 16 OMe Cl K2C03 1 6 6

Claims (46)

  1. A method for performing an olefin metathesis or a cross-coupling reaction, characterised in that the method is performed in the presence of a catalyst system comprising, a) a source of a d-block metal, b) optionally a promoter, an activator and/or a base, and c) a source of a 3-membered carbocyclic ligand.
  2. 2. A method as claimed in claim 1, wherein the d-block metal is a Group VIII metal or Cu.
  3. 3 A method as claimed in claim 2, wherein the d-block metal is selected from Ru, Rh, Ni, Pd or Pt.
  4. 4. A method as claimed in any one of the preceding claims, wherein the 3-membered carbocyclic ligand comprises a group of formula wherein (i) R' and R2 are independently selected from hydrocarbyl or heterohydrocarbyl groups, or (ii) R1 and R', together with the carbons to which they are attached, form a five, six, seven or eight membered ring.
  5. A method as claimed in claim 4, wherein the hydrocarbyl groups are selected from alkyl, aryl, alkenyl or alkynyl groups.
  6. 6. A method as claimed in claim 5, wherein the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, t-butyl and adamantyl.
  7. 7. A method as claimed in claim 5, wherein the aryl group is selected from phenyl, ortho-tolyl, meta-tolyl, para-tolyl, ethyiphenyl, isopropylphenyl, t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,5- dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropyiphenyl, naphthyl and benzyl.
  8. 8 A method as claimed in claim 4, wherein at least one heterohydrocarbyl group is attached directly to the 3-membered ring.
  9. 9. A method as claimed in claim 8, wherein the heterohydrocarbyl group is of formula -Z(R3). wherein Z is selected from Si, N, P, 0 or 5, m is 1 to 4, and wherein the groups R3 may be the same or different and each is a hydrocarbyl group.
  10. 10. A method as claimed in claim 4, wherein at least one heterohydrocarbyl group is not attached directly to the 3-membered ring.
  11. 11. A method as claimed in claim 10, wherein at least one heterohydrocarbyl group is selected from CF3, CF2CF3, CH2OMe, CH2NMe2, CH2CH2NH2, CH2CH2N(R1)2, CH2CH2P(R1)2, CH2CH2CH2P(R1)2, fluorophenyl, perfluorophenyl, chlorophenyl, bromophenyl, C6H4(CF3), C6H3(CF3)2, C6H4(OMe), C5H3(OMe)2, C6H4(N(R1)2), C6H4(P(R1)2), where R1 is as defined in claim 4.
  12. 12. A method as claimed in claim 4, wherein R' and/or R2 are such that the 3-membered carbocyclic ligand is a multidentate ligand.
  13. 13. A method as claimed in claim 12, wherein R and/or R' are of formula CH2CH2P(R)L wherein R is a hydrocarbyl group.
  14. 14. A method as claimed in any one of the preceding claims, wherein the catalyst system is formed in situ during the reaction.
  15. 15. A method as claimed in any one of claims ito 13, wherein the catalyst system is pre-formed.
  16. 16. A method as claimed in claim 15, wherein the catalyst system comprises a compound of formula wherein M is a d-block metal, n is 0 to 5 and the L groups, which may be the same or different, are ligands.
  17. 17. A method as ciaimed in ciaim i6, wrierein the L groups are stabilising ligands selected from chloride, bromide, iodide, hydride, alkoxide, amide, acetate, acetylacetonate, amine, ether, water, phosphines, pyridine, alkene, alkyne and N-heterocyclic carbenes.
  18. 18. A method as claimed in claim 16, wherein the L groups are reactive ligands selected from alkyl, aryl, carbene, alkylidene.
  19. 19. A method as claimed in claim 16, wherein at least one L is a substrate molecule for the reaction.
  20. 20. A method as claimed in claim 16, wherein at least one L is a 3-membered carbocyclic ligand, giving a compound of formula M(L wherein the L groups which may be the same or different, are ligands, p is 0 to 5, and R4 and R are as defined for R1 and R2 in ciaim 4.
  21. 21. A method as claimed in any one of the preceding claims, wherein the olefin metathesis reaction is selected from cross-metathesis, nng closing metathesis, enzyme metathesis, ring opening metathesis, ring opening metathesis polymerisation, acyclic diene metathesis or alkyne metathesis.
  22. 22. A method as claimed in any one of claims 1 to 20, wherein the cross-coupling reaction is selected from reactions with organoboron compounds, reactions with organotin compounds, reactions with organozinc compounds, reactions with organomagnesium compounds, reactions with other organometallic compounds, reactions with allylic compounds, reactions with conjugated diene compounds, carbometallation reactions, reactions with alkyne compounds, reactions with olefinic compounds, reactions involving a cyclometallation step and reactions for the formation of carbonheteroatom bonds.
  23. 23. A catalyst system for catalysing olefin metathesis or cross-coupling reactions, the catalyst system comprising, a) a source of a d-block metal, b) optionally a promoter, an activator and/or a base, and c) a source of a 3-membered carbocyclic ligand.
  24. 24. A catalyst system as claimed in claim 23, wherein the d-block metal is a Group VIII metal or Cu.
  25. 25. A catalyst system as claimed in claim 24, wherein the d-block metal is selected from Ru, Rh, Ni, Pd or Pt.
  26. 26. A catalyst system as claimed in any one of claims 23 to 25, wherein the 3-membered carbocyclic Iigand comprises a group of formula : wherein (i) R and R are independently selected from hydrocarbyl or heterohydrocarbyl groups, or (ii) R' and R2, together with the carbons to which they are attached, form a five, six, seven or eight membered ring.
  27. 27. A catalyst system as ciaimed in claim 26, wherein the hydrocarbyl groups are selected from alkyl, aryl, alkenyl or alkynyl groups.
  28. 28. A catalyst system as claimed in claim 27, wherein the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, t-butyl and adamantyl.
  29. 29. A catalyst system as claimed in claim 27, wherein the aryl group is selected from phenyl, ortho-tolyl, meta-tolyl, para-tolyl, ethyl phenyl, isopropylphenyl, t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, naphthyl and benzyl.
  30. 30. A catalyst system as claimed in claim 26, wherein at least one heterohydrocarbyl group is attached directly to the 3-membered ring.
  31. 31. A catalyst system as claimed in claim 30, wherein the heterohydrocarbyl group is of formula -Z(R3)rn wherein Z is selected from Si, N, F, 0 or S and M is I to 4, and wherein the groups may be the same or different and each is a hydrocarbyl group.
  32. 32. A catalyst system as claimed in claim 26, wherein at least one heterohydrocarbyl group is not attached directly to the 3-membered ring.
  33. 33. A catalyst system as claimed in claim 32, wherein at least one heterohydrocarbyl group is selected from CF3, CF2CF3, CH2OMe, CH2NMe2, CH2CH2NH2, CH2CH2N(R1)2, CH2CH2P(R1)2 CH2CH2CH2P(R1)2, fluorophenyl, perfluorophenyl, chlorophenyl, bromophenyl, C6H4(CF3), C6H3(CF3)2, C5H4(OMe), C5H3(OMe)2, C5H4(N(R1)2), C6H4(P(R1)2), where R1 is as defined in claim 4.
  34. 34. A catalyst system as claimed in claim 26, wherein R and/or R2 are such that the 3-membered carbocyclic ligand is a multidentate ligand.
  35. A catalyst system as claimed in claim 34, wherein R' and/or R2 are of formula CH2CH2P(R)2 wherein R is a hydrocarbyl group.
  36. 36. A catalyst system as claimed in any one of claims 23 to 35, wherein the catalyst system comprises a compound of formula wherein M is a d-block metal, n is 0 to 5 and the L groups, which may be the same or different, are ligands.
  37. 37. A catalyst system as claimed in claim 36, wherein the L groups are stabilising ligands selected from chloride, bromide, iodide, hydride, alkoxide, amide, acetate, acetylacetonate, amine, ether, water, phosphine, pyridine, alkene, alkyne and N-heterocyclic carbenes.
  38. 38. A catalyst system as claimed in claim 36, wherein the L groups are reactive ligands selected from akyl, aryl, carbene and alkylidene.
  39. 39 A catalyst system as claimed in claim 36, wherein at least one L is a substrate molecule for the reaction.
  40. 40. A catalyst system as claimed in claim 36, wherein at least one L is a 3-membered carbocyclic ligand, giving a compound of formula M(L1 wherein the L groups which may be the same or different, are ligands, p is 0 to 5, and R and R' are as defined for R1 and R in claim 4.
  41. 41. A method for producing a catalyst system for catalysing olefin metathesis or cross-coupling reactions, the method comprising combining a) a source of a d-block metal, b) optionally, a further reagent, c) a source of a 3-membered carbocyclic ligand.
  42. 42. A method as claimed in claim 41, wherein the further reagent is selected from one or more of a base, an acid, a reducing agent, an oxidising agent or a ligand.
  43. 43. A method as claimed in claim 42, wherein the base is selected from one or more amines, amides, alkoxides, hydroxides, carbonates and BuLi.
  44. 44. A method as claimed in any one of claims 41 to 43, wherein the source of a d-block metal is selected from the appropriate elemental metal, the elemental metal dispersed on a suitable carrier material or a metal complex of formula MLq where M and L are as defined in claim 16 and qisan integerof 1 to6.
  45. 45. A method as claimed in any one of claims 41 to 44, wherein the source of a 3-membered carbocyclic ligand is selected from the free carbene ligand of formula R2; a carbene ligand stabilised by coordination to a Lewis acid fragment of formula wherein Z is a Lewis acid fragment; or a substituted 3,3 cyclopropene compound of formula :: wherein the X groups may be the same or different and are selected from halide, pseudohalide, weakly coordinating anion, H, a main group metal, a main group metal fragment or a d-block metal fragment MLq as defined in claim 44.
  46. 46. Use of a catalyst system as claimed in any one of claims 23 to 40 to catalyse an olefin metathesis or a cross-coupling reaction.
GB0703509A 2007-02-23 2007-02-23 Catalytic olefin metathesis reaction method Withdrawn GB2447068A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
GB0703509A GB2447068A (en) 2007-02-23 2007-02-23 Catalytic olefin metathesis reaction method
PCT/GB2008/000619 WO2008102157A1 (en) 2007-02-23 2008-02-21 Catalytic method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB0703509A GB2447068A (en) 2007-02-23 2007-02-23 Catalytic olefin metathesis reaction method

Publications (2)

Publication Number Publication Date
GB0703509D0 GB0703509D0 (en) 2007-04-04
GB2447068A true GB2447068A (en) 2008-09-03

Family

ID=37945592

Family Applications (1)

Application Number Title Priority Date Filing Date
GB0703509A Withdrawn GB2447068A (en) 2007-02-23 2007-02-23 Catalytic olefin metathesis reaction method

Country Status (2)

Country Link
GB (1) GB2447068A (en)
WO (1) WO2008102157A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220220239A1 (en) * 2019-05-27 2022-07-14 The University Of Tokyo Polar group-containing olefin copolymer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0118801A2 (en) * 1983-03-09 1984-09-19 Sumitomo Chemical Company, Limited A catalyst for isomerization reaction
WO1993020111A2 (en) * 1992-04-03 1993-10-14 E.I. Du Pont De Nemours And Company Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization
US20060173145A1 (en) * 2005-02-01 2006-08-03 Pawlow James H Multi-functionalized high-trans elastomeric polymers

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58154594A (en) * 1982-03-09 1983-09-14 Zenichi Yoshida Cyclopropenylidene complex

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0118801A2 (en) * 1983-03-09 1984-09-19 Sumitomo Chemical Company, Limited A catalyst for isomerization reaction
WO1993020111A2 (en) * 1992-04-03 1993-10-14 E.I. Du Pont De Nemours And Company Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization
US20060173145A1 (en) * 2005-02-01 2006-08-03 Pawlow James H Multi-functionalized high-trans elastomeric polymers

Also Published As

Publication number Publication date
GB0703509D0 (en) 2007-04-04
WO2008102157A1 (en) 2008-08-28

Similar Documents

Publication Publication Date Title
Hameury et al. Metal complexes with oxygen-functionalized NHC ligands: synthesis and applications
Partyka Transmetalation of unsaturated carbon nucleophiles from boron-containing species to the mid to late d-block metals of relevance to catalytic C− X coupling reactions (X= C, F, N, O, Pb, S, Se, Te)
Decker et al. Homogeneous catalytic transfer semihydrogenation of alkynes–an overview of hydrogen sources, catalysts and reaction mechanisms
Khramov et al. N-Heterocyclic carbenes: deducing σ-and π-contributions in Rh-catalyzed hydroboration and Pd-catalyzed coupling reactions
US20030109713A1 (en) Process for the catalytic synthesis of biaryls and polymers from aryl compounds
Schneider et al. Pyridin‐, Quinolin‐and Acridinylidene Palladium Carbene Complexes as Highly Efficient C–C Coupling Catalysts
Hazari et al. Dinuclear Pd I complexes with bridging allyl and related ligands
Zinn et al. 10 Carbenes: reactivity and catalysis
Lee et al. Polyhedral oligomeric silsesquioxane-conjugated bis (diphenylphosphino) amine ligand for chromium (III) catalyzed ethylene trimerization and tetramerization
Ahmed et al. A K-arylacetylide complex for catalytic terminal alkyne functionalization using KO t Bu as a precatalyst
Herrmann et al. Synthesis, structure and catalytic application of palladium (II) complexes bearing N-heterocyclic carbenes and phosphines
Barnett et al. Air-Stable [(R3P) PdCl2] 2 Complexes of Neopentylphosphines as Cross-Coupling Precatalysts: Catalytic Application and Mechanism of Catalyst Activation and Deactivation
Miranda-Pizarro et al. Reductive C–C Coupling from Molecular Au (I) Hydrocarbyl Complexes: A Mechanistic Study
Ostrowska et al. Selective dimerization of terminal acetylenes in the presence of PEPPSI precatalysts and relative chloro-and hydroxo-bridged N-heterocyclic carbene palladium dimers
Lin et al. C− H Bond Activation and Subsequent C (sp2)− C (sp3) Bond Formation: Coupling of Bromomethyl and Triphenylphosphine in an Iridium Complex
US6316675B1 (en) Process for the preparation of an olefin-substituted aromatic or heteroaromatic compound
GB2447068A (en) Catalytic olefin metathesis reaction method
Günay et al. Synthesis, X-ray structures, and catalytic activities of (κ2-C, N)-palladacycles bearing imidazol-2-ylidenes
Štepnicka 1’-Functionalised ferrocene phosphines: Synthesis, coordination chemistry and catalytic applications
Cai et al. Cobalt-mediated direct carbon-hydrogen bond functionalizations
Crociani et al. Palladium complexes of 8-(di-tert-butylphosphinooxy) quinoline
Crociani et al. Mechanistic study on the cross-coupling of alkynyl stannanes with aryl iodides catalyzed by η 2-(dimethyl fumarate) palladium (0) complexes with iminophosphine ligands
Lehtonen Dioxotungsten (VI) complexes with tetradentate [O, N, N, O] ligands: syntheses, spectral characterisation and catalytic applications
Singh et al. N-Heterocyclic carbenes: Advances in transition metal and organic catalysis
Slaughter Catalysis with acyclic aminocarbene ligands: Alternatives to NHCs with distinct steric and electronic properties

Legal Events

Date Code Title Description
WAP Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1)