WO2008102157A1 - Procédé de catalyse - Google Patents

Procédé de catalyse Download PDF

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Publication number
WO2008102157A1
WO2008102157A1 PCT/GB2008/000619 GB2008000619W WO2008102157A1 WO 2008102157 A1 WO2008102157 A1 WO 2008102157A1 GB 2008000619 W GB2008000619 W GB 2008000619W WO 2008102157 A1 WO2008102157 A1 WO 2008102157A1
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catalyst system
groups
group
formula
reactions
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PCT/GB2008/000619
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English (en)
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Michael Green
Duncan Frank Wass
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The University Of Bristol
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    • 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
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    • 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
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Definitions

  • the present invention relates to methods for 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.
  • ligands based on cyclic heteroatom- stabilised C-donors have also been described, such ligands often being called N-heterocyclic carbenes (W.A. Herrmann, C. K ⁇ cher, 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 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 3-membered carbocyclic ligand or a source of a 3-membered carbocyclic ligand.
  • 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 3-membered carbocyclic ligand or 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 VlII 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.
  • the most preferred d- block metals are Pd and Ru. Pd is particularly suitable for cross-coupling reactions and Ru for metathesis reactions.
  • the 3-membered carbocyclic ligand comprises a group of formula
  • R 1 and R 2 are independently selected from hydrocarbyl or heterohydrocarbyl groups, or (ii) R 1 and R 2 , 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 hydrocarbyl groups are alkyl, for example methyl, ethyl, n- propyl, isopropyl, t-butyl, adamantyl; aryl or substituted aryl, for example phenyl, ortho-to ⁇ y ⁇ , meta-tolyl, para-tolyl, ethylphenyl, isopropylphenyl, t- butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 2,6- diisopropylphenyl, 2,4,6-trimethylphenyI, 2,4,6-triisopropylphenyl, naphthyl, benzyl, alkenyl or alkynl groups.
  • Suitable heterohydrocarbyl groups may have one or more heteroatoms 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 ring are: -Z(R 3 ) m where Z is Si and m is 3, Z is N and m is 2, Z is P and m is 2, Z is O and m is 1 , or Z is S and m is 1 ; the groups R 3 are the same or different hydrocarbyl groups as defined above.
  • Suitable examples where the heteroatom(s) are in other positions are: CF 3 , CF 2 CF 3 , CH 2 OMe, CH 2 NMe 2 , CH 2 CH 2 NH 2 , CHzCHzNCR 1 ⁇ , CH 2 CH 2 P(R 1 ) 2 , CH 2 CH 2 CH 2 P(R 1 ) 2 , fluorophenyl, perfluorophenyl, chlorophenyl, bromophenyl, C 6 H 4 (CF 3 ), C 6 H 3 (CF 3 ) 2 , C 6 H 4 (OMe), C 6 H 3 (OMe) 2 , C 6 H 4 (N(R 1 ) 2 ),-C 6 H 4 (P(R 1 ) 2 ), where -R 1 is as defined above.
  • R 1 and R 2 these groups may themselves act as supporting ligands to the metal, for example when R 1 is CH 2 CH 2 P(R 1 ) 2 the P- atom of this group may donate to the metal as a phosphine donor ligand.
  • R 1 and/or R 2 are such that the 3-membered carbocyclic ligand is a multidentate ligand.
  • R 1 and R 2 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. Whether or not the catalyst system is pre-formed, the 3-membered carbocyclic ligand will be present.
  • the catalyst system may, preferably, comprise a compound of formula
  • M is a d-block metal
  • n is 0 to 5
  • 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:
  • the catalyst system may comprise a compound of formula
  • X groups which may be the same or different, are halide or pseudohalide and L 2 is PR3, wherein each R is independently selected from hydrocarbyl or H. Most preferred is when both X are chloride and L 2 is PPh 3 or PBu 3 .
  • the catalyst system may comprise a compound of formula
  • M is a d-block metal
  • the X groups which may be the same or different, are halide or pseudohalide.
  • the preferred d-block metal is Pd and the preferred X groups are Cl.
  • the preferred R 1 and R 2 groups are all phenyl or all Pr 2 N 1 .
  • Such a catalyst system is particularly suitable for cross-coupling reactions.
  • the most preferred compounds according to this general formula are the palladium complexes 3
  • the catalyst system may, in the alternative, comprise a compound of one of the formulae:
  • each R is a hydrocarbyl group or H or wherein two R groups, together with the carbon to which they are both attached, form a ring or multiple ring system, and the X 1 groups, which may be the same or different, are halide or pseudohalide.
  • the preferred X 1 is a halide, most preferably choride.
  • Such a catalyst system is particularly suitable for metathesis reactions.
  • the most preferred ruthenium complex is 5 bis(triphenyl phosphine)-3-phenyl-1 H-inden- 1-ylidene ruthenium III dichloride
  • the olefin metathesis reaction may be selected from cross-metathesis, ring closing metathesis, enyne metathesis, ring opening metathesis, ring opening metathesis polymerisation, acyclic diene metathesis or alkyne metathesis.
  • the cross-coupling reaction may be selected from:
  • 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 0 C and 25O 0 C, preferably between O 0 C and 200 0 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.
  • the catalyst may be in the solid phase by heterogenisation on a suitable carrier such as a polymer, silica, carbon, alumina, etc.
  • a catalyst promoter 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.
  • a promoter is usually not required, although in some specific cases one may be required to generate an active system.
  • 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 3-membered carbocyclic ligand or a source of a 3-membered carbocyclic ligand.
  • 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 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).
  • a base for example: amines, amides, alkoxides, hydroxides, carbonates, BuLi or similar reagents
  • an acid for example: amines, amides, alkoxides, hydroxides, carbonates, BuLi or similar reagents
  • a reducing agent for example: amines, amides, alkoxides, hydroxides, carbonates, BuLi or similar reagents
  • an acid for example: amines
  • 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 3-membered carbocyclic ligand or 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 ML m , 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-membered carbocyclic ligand source is where the ligand has been stabilized by co-ordination to a Lewis acid fragment, as illustrated:
  • Z is a suitable Lewis acid, for example a main group Lewis acid such as a borane (e.g. BH 3 , BCI 3 , BL 3 and the like), appropriate group 13 compounds (e.g. AICI 3 ), appropriate group 14 compounds, (e.g. stannanes, SnCI 2 , SnCI 4 and the like), appropriate group 15 compounds (e.g. SbFs); or a further transition metal compound ML m , as defined above.
  • a borane e.g. BH 3 , BCI 3 , BL 3 and the like
  • appropriate group 13 compounds e.g. AICI 3
  • appropriate group 14 compounds e.g. stannanes, SnCI 2 , SnCI 4 and the like
  • appropriate group 15 compounds e.g. SbFs
  • ML m a further transition metal compound
  • the X groups may be the same or different and may be a halide (F, Cl, Br, I, etc), pseudo-halide (e.g. N 3 ' , CN “ , NCO ' , OCN “ , etc.) or weakly- coordinating anion (e.g. BF 4 , PF 6 , CIO 4 , AsF 6 , AICI 4 , B(C 6 F 5 ) 4 , etc), H, a main group metal or main group metal fragment (e.g. Li, Na, K, MgCI) or transition metal fragment ML m as defined above.
  • a main group metal or main group metal fragment e.g. Li, Na, K, MgCI
  • transition metal fragment ML m 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 (e.g. Pd metal, [Pd(PPh 3 )J, [RhCI(PPh 3 ) 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.
  • 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.
  • 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 Ci to C 32 , more preferably C 1 to C 24 , most preferably Ci to C 18 .
  • Heterohydrocarbyl refers to a group as defined above for hydrocarbyl but containing one or more heteroatoms preferably selected from Si, P, N, O, S and F.
  • Alkyl is preferably Ci to CQ, more preferably straight chain Ci to C 6 in particular methyl, ethyl, n-propyl or n-butyl.
  • Halide is fluoride, chloride, bromide or iodide.
  • Pseudohalides are groups which resemble halides in their chemistry and include N 3 " , CN “ , NCO “ , OCN “ , and SCN “ .
  • the invention is illustrated by the Figure which is a single crystal X-ray diffraction structure of the compound described in Example 2.
  • 2,3-Di(diisopropylamino)cyclopropenium tetrafluoroborate was prepared following the procedure of Bertrand and co-workers (Science, 2006, 312, 722).
  • the reaction was conducted in the presence of a catalyst.
  • Bis(triphenylphosphine)-3-phenyl-1 H-inden-1-ylideneruthenium (II) dichloride was prepared as reported by Mynott and co-workers (Chemistry - A European Journal, 2001 , 7, 4811).
  • Bis(dipropylamino)cyclopropenium tetraphenyl borate (0.122g, 0.219 mmol) and potassium bis(trimethylsilyl)amide (0.44 mL, 0.219 mmol) were placed in a Schlenk flask and cooled to -78 0 C. THF (5 mL) was added slowly and the mixture stirred at that temperature for 10 min.

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Abstract

L'invention concerne des procédés destinés à la réalisation d'une réaction de couplage croisé ou de métathèse d'oléfines, les procédés étant mis en oeuvre en présence d'un système catalyseur comprenant une source d'un métal du bloc d, une source d'un ligand carbocyclique à 3 éléments et, éventuellement, un promoteur, un activateur et/ou une base. L'invention concerne également les systèmes catalyseurs, des procédés de production de ces systèmes catalyseurs et les applications de ces systèmes catalyseurs dans la catalyse d'une réaction de couplage croisé ou de métathèse d'oléfines.
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JP2020193340A (ja) * 2019-05-27 2020-12-03 国立大学法人 東京大学 極性基含有オレフィン共重合体
CN113874402A (zh) * 2019-05-27 2021-12-31 国立大学法人东京大学 含极性基团的烯烃共聚物

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