WO1999011648A1 - Composes organometalliques et leur procede de preparation et d'utilisation - Google Patents

Composes organometalliques et leur procede de preparation et d'utilisation Download PDF

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WO1999011648A1
WO1999011648A1 PCT/GB1998/002548 GB9802548W WO9911648A1 WO 1999011648 A1 WO1999011648 A1 WO 1999011648A1 GB 9802548 W GB9802548 W GB 9802548W WO 9911648 A1 WO9911648 A1 WO 9911648A1
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formula
compound
group
alkyl
aryl
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PCT/GB1998/002548
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English (en)
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Colin White
Paul Beagley
Philip John Davies
Andrew John Blacker
Ben James Mellor
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Zeneca Limited
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Priority to AU88716/98A priority Critical patent/AU8871698A/en
Publication of WO1999011648A1 publication Critical patent/WO1999011648A1/fr

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    • 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
    • C07F17/00—Metallocenes
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • the present invention relates to organometallic compounds, more particularly to optically active organometallic compounds, their use as catalysts, methods for their preparation and their use in synthesis particularly in asymmetric synthesis.
  • organometallic compounds which achieve one or more of the objectives of being relatively inexpensive to prepare, effective catalysts for use in organic syntheses, particularly asymmetric syntheses and which are less sensitive to oxygen. According to a first aspect of the present invention there is provided an organometallic compound of Formula(1):
  • R 1 , R 2 , R 3 , and R 4 each independently is -H or optionally substituted alkyl or optionally substituted aryl; or one of R 1 and R 2 or R 2 and R 3 or R 3 and R 4 together with the atoms to which they are attached forms a 5- or 6- membered ring;
  • R 5 , R 6 , R 7 and R 8 each independently is -H or optionally substituted alkyl or optionally substituted aryl, or is a group of formula -Si(R 11 ) 3 , -P(R 12 ) 2 or -N(R 13 ) 2 , where each R 11 , R 12 and R 13 independently represents alkyl or aryl, provided that at least one of
  • R 5 , R 6 , R 7 and R 8 is a substituted or unsubstituted alkyl group comprising 5 or more carbon atoms and which is branched at the carbon alpha to the cyclopentadienyl ring or is a group of formula -Si(R 1 ) 3 , -P(R 12 ) 2 or -N(R 13 ) 2 ; R 9 and R 10 each independently is optionally substituted alkyl or aryl; M is a metal selected from the group consisting of Ti, Zr and Hf; n is 2; and
  • X is halo or aryloxy, or (X) n may with the metal atom to which it is attached form a 5, 6 or 7-membered ring.
  • ring A the cyclopentadienyl ring bearing the groups R 1 -R 4 shall be referred to as ring A
  • ring B the cyclopentadienyl ring bearing the groups R 5 -R 8 shall be referred to as ring B.
  • Alkyl groups which may be represented by R ⁇ R 2 , R 3 , R 4 , R 9 , R 10 R 11 , R 12 and R 13 are preferably C 1-6 -alkyl, more preferably a C ⁇ -alkyl and especially methyl or ethyl groups.
  • Aryl groups which may be represented by R 1 , R 2 , R 3 , R 4 , R 9 , R 10 R 11 , R 12 and R 13 are preferably phenyl or naphthyl, more preferably phenyl groups.
  • each of R 1 , R 2 , R 3 and R 4 represents an alkyl group, particularly a C 1-4 alkyl group and especially a methyl group.
  • At least one of R 5 to R 8 represents a substituted or unsubstituted alkyl group comprising 5 or more carbon atoms and which is branched at the carbon alpha to the cyclopentadienyl ring or is a group of formula -Si(R 11 ) 3 , -P(R 12 ) 2 or -N(R 13 ) 2 , the remainder being H or alkyl or aryl groups as defined above for R 1 -R 4 .
  • Substituted or unsubstituted alkyl groups comprising 5 or more carbon atoms and which are branched at the carbon alpha to the cyclopentadienyl ring are preferred, and examples which may be represented by R 5 to R 8 include non-cyclic and cyclic groups.
  • the total number of carbon atoms is often no more than 30 and commonly no more than 20.
  • non-cyclic groups examples include 2-pentyl, tert-pentyl, 2-hexyl, tert-hexyl, 2-heptyl, tert-heptyl, 2-octyl, tert- heptyl, 2-nonyl, tert-nonyl, diphenylmethyl and triphenylmethyl groups.
  • cyclic groups include cyclopentyl, cyclohexyl and indenyl groups, and groups derived from alkaloids such as camphor, borneol, fenchol, pinene, verbenol and iso-menthol.
  • Preferred cyclic groups include menthyl and neomenthyl groups.
  • the alkyl group comprising 5 or more carbon atoms and which is branched at the carbon alpha to the cyclopentadienyl ring which may be represented by
  • R 5 to R 8 is an enantiopure auxiliary.
  • the enantiopure auxiliary provides steric discrimination and diastereoisomeric complexes that allow physical separation, and may be any asymmetric group.
  • the enantiopure auxiliary is preferably menthyl or neomenthyl, more preferably (-)-menthyl and (+)-neomenthyl.
  • Groups of Formula -Si(R 11 ) 3 , -P(R 12 ) 2 or -N(R 13 ) 2 , which may be represented by R 5 to R 8 include t-butyldimethylsilyl, trimethylsilyl, triphenylsilyl, t-butyldiphenylsilyl, diphenylphosphinyl, diphenylamino and piperidinyl.
  • each of R 1 to R 8 are chosen such that the pattern of substitution around cyclopentadienyl ring B is different from that of cyclopentadienyl ring A.
  • R 5 , R 6 , R 7 , and R 8 represents an alkyl group comprising 5 or more carbon atoms and which is branched at the carbon alpha to the cyclopentadienyl ring, or is a group of formula -Si(R 11 ) 3 , -P(R 12 ) 2 or -N(R 13 ) 2 , where R 11 , R 12 and R 13 are as defined above.
  • R 5 , R 6 , R 7 , and R 8 represent an alkyl group comprising 5 or more carbon atoms and which is branched at the carbon alpha to the cyclopentadienyl ring, or are groups of formula -Si(R 1 ) 3 , -P(R 12 ) 2 or -N(R 13 ) 2 , it is especially preferred that the two groups so defined are selected from the pairings R 5 and R 6 , R 5 and R 7 , R 6 and R 8 or R 7 and R 8 .
  • R 5 , R 6 , R 7 , and R 8 represents an alkyl group comprising 5 or more carbon atoms and which is branched at the carbon alpha to the cyclopentadienyl ring, or is a group of formula -Si(R 11 ) 3 , -P(R 12 ) 2 or -N(R 13 ) 2
  • R 6 or R 7 represents menthyl or neomenthyl, and more preferably (-)-menthyl and (+)-neomenthyl, and that the remainder of R 5 to R 8 represent H.
  • the substituent is often selected from -F, -Cl, -Br, -I, alkyl, preferably C 1-4 alkyl, aryl, alkoxy, preferably C M alkoxy, -NO 2 , -CN, -OH, -NHSO 2 CH 3 , -NHSO 2 aryl or -NR 14 R 15 in which R 14 and R 15 each independently are -H, methyl, ethyl, phenyl or benzyl.
  • Preferred substituents include alkyl, especially C 1-4 alkyl, phenyl, alkoxy, especially C 1-4 alkoxy, NHSO 2 CH 3 , -NHSO 2 phenyl or -NR 14 R 15 in which R 14 and R 15 each independently are -H, methyl, ethyl, phenyl or benzyl.
  • the groups represented by R 1 to R 3 are unsubstituted or are substituted only by alkyl or aryl substituents.
  • the metal represented by M is preferably titanium.
  • the halo represented by X is preferably -F, -Cl or -Br.
  • the aryloxy represented by X is preferably phenoxy or naphthoxy, more preferably phenoxy.
  • (X) n together with M forms a 5, 6 or 7-membered ring
  • (X) n preferably, comprises two O or S, or one O and one S, atoms coordinated to M, preferably two O atoms.
  • (X) n together with M is a 5-membered ring, especially where (X) n is a catechol or a dihydroxynaphthalene.
  • Especially preferred compounds of Formula (1) are those in which R 1 to R 4 are all methyl, R 5 and R 8 are both -H, R 6 is menthyl or neomenthyl, R 7 is -H, R 9 and R 0 are both methyl, M is titanium and X is -Cl.
  • the compound of Formula (1) may be prepared by reaction of a compound of Formula (2), or isomers thereof in which the cyclopentadienyl double bonds are in different positions around the rings:
  • Formula (2) first with an organometallic compound and secondly with a compound of formula M(X) ⁇ X 1 in which R 1 to R 10 , X and n are as hereinbefore defined and X 1 is halo.
  • X 1 is preferably -Cl, -Br or -I, more preferably -F or -Cl.
  • the organometallic compound is preferably an organolithium compound, more preferably an alkyllithium compound and especially n-butyllithium.
  • the compound of Formula (1) is preferably prepared in a liquid medium.
  • the liquid medium is preferably an ether, more preferably a diaikyl ether such as a diethyl ether or a cyclic ether such as tetrahydrofuran (THF).
  • the liquid medium is preferably dried before use.
  • the organometallic compound is preferably added to the compound of Formula (2) at a temperature of from -30°C to 10°C, more preferably at. from -10°C to 0°C.
  • the compound of formula M(X) n X 1 is preferably added to the reaction mixture after cooling the reaction mixture to a temperature of from -100°C to -50°C, more preferably at from -80°C to -70°C.
  • the reaction temperature may then be increased to 20°C to 60°C, or conveniently to the boiling point of the liquid medium.
  • the preparation of the compound of Formula (1) is preferably carried out in an inert atmosphere of for example nitrogen or argon.
  • the compound of Formula (1) may be isolated from the reaction mixture by any convenient means for example by adding an acid such as hydrochloric acid and separating the organic and aqueous layers followed by evaporation of the liquid medium.
  • the compound of Formula (1) may be purified by any convenient means for example by flash chromatography or distillation under reduced pressure.
  • the process for preparing compounds of Formula (1) provides a second aspect of the present invention.
  • the compounds of Formula (2) may be prepared by reaction of a compound of Formula (3) or isomers thereof in which the cyclopentadienyl double bonds are in different positions around the rings:
  • R 1 to R 10 and X 1 are as hereinbefore defined.
  • the compound of Formula (4) preferably in a liquid medium, more preferably in an ether such as THF, is firstly reacted with an organometallic compound preferably an organolithium compound, more preferably an alkyllithium compound and especially n-butyllithium at a temperature of from -20°C to 10°C and secondly with a compound of Formula (3) preferably at a temperature from 20°C to 60°C and conveniently at the boiling point of the liquid medium.
  • the compound of Formula (2) may be isolated by removing the precipitated lithium chloride by filtration and evaporating the liquid medium. Any excess compound of Formula (3) may be removed by heating under reduced pressure.
  • the compound of Formula (3) may be prepared by reacting a compound of
  • organometallic compound preferably an organolithium compound, more preferably an alkyllithium compound and especially n-butyllithium and then with a compound represented by CI 2 SiR 9 R 10 in which R 9 and R 0 are as hereinbefore defined.
  • the compound of Formula (3) may be recovered and purified by any convenient means such as distillation.
  • the compound of Formula (4) may be prepared by reaction of a cyclopentadienyl salt with an alkylating agent, particularly an alkylating agent comprising an enantiopure auxiliary, such as menthyl tosylate or neomenthyl tosylate.
  • the cyclopentadienyl salt is formed from the corresponding cyclopentadiene and an alkyllithium such as butyllithium, a metal hydride, such as an alkali metal hydride, particularly sodium hydride, or an alkali metal such as sodium, sodium metal being preferred.
  • the cyclopentadiene is preferably freshly prepared before use by cracking dicyclopentadiene.
  • the compound of Formula (5) may be prepared by reducing the corresponding cyclopent-2-enone with a reducing agent or by the method of Garner et al, Tett. Letts. 35, 16, 2463.
  • Suitable reducing agents include lithium aluminium hydride, lithium diisobutyl aluminium hydride or preferably a combination of sodium borohydride with a lanthanyl halide such as CeCI 3 .
  • the compound of Formula (4) may be isolated and purified by distillation.
  • This interconversion process is also applicable to compounds having the same general formula as those of Formula (1) except that both of the pairings R 1 and R 2 and R 3 and R 4 together with the carbon atoms to which they are attached form a phenyl ring, such that ring A comprises part of a fluorenyl moiety, R 5 and R 8 are both -H, R 6 is menthyl or neomenthyl, R 7 is -H, R 9 and R 10 are both methyl, M is titanium and X is -Cl.
  • This process of conversion of less active isomer to more active isomer forms a third aspect of the present invention.
  • the conversion is preferably achieved by irradiating the less active isomer with uv-visible light having wavelengths in the range of from 200nm to 800nm, and preferably from 220nm to 450nm.
  • a uv-visible lamp emitting the desired wavelength range is preferably employed.
  • the conversion preferably takes place with the less active isomer dissolved in an inert hydrocarbon solvent such as benzene, toluene, xylene, hexane or heptane, and at ambient or sub-ambient temperature, such as no less than -40°C particularly no less than -25°C, and up to no more than 25°C, such as no more than 10°C. It has been found that often the less active isomer is the R isomer.
  • the product so obtained can be treated by the uv-visible process of conversion to convert substantially all of the less active isomer to the more active isomer.
  • a suitable solvent for example a hydrocarbon solvent such as hexane. Temperatures of from 0°C to -40°C may be employed.
  • a further method of separating the R from the S isomer is by HPLC, for example using a cyclodextrin column such as Chiralcel CDTM, available from Daicel Inc., using mixtures of alkane, preferably hexane, and ether, preferably t-butylmethyl ether.
  • the less active isomer obtained by crystallisation or HPLC can then be converted to the more active isomer by the use of the uv-visible process of conversion.
  • the compounds are useful as catalysts for a number of asymmetric syntheses such as in hydrogenations, alkylations, hydrosilylations, polymerisations and cycloadditions.
  • Use of these compounds as catalysts generally has the advantage that mild reaction conditions may be used and that high yields and good enantiomeric excesses (ee) may be obtained.
  • the use of a compound of Formula (1) as a catalyst forms a further feature of the present invention.
  • a process for asymmetric hydrogenation of a compound having a double or triple bond which comprises reacting the compound with hydrogen in the presence of a compound of Formula (1).
  • Compounds having a double bond which may be asymmetrically hydrogenated include alkenes, imines, vinylamides, ketones and vinylesters, and particularly alkenes, ketones and imines.
  • the asymmetric hydrogenation is preferably carried out in a liquid medium.
  • suitable liquid media include alkanes and arenes. Where the liquid medium is an alkane it is preferably a C 5 . 15 -alkane, more preferably n-hexane, n-heptane, isomers of octane, cyclohexane or decalin. Where the liquid medium is an arene it is preferably toluene, xylene or mesitylene. It has surprisingly been found that the addition of water, for example at an amount up to 1 equivalent based on the catalyst can increase the enantiomeric excess of one of the isomers of the asymmetric reaction product. Hydrogen gas is preferably used in the hydrogenation process.
  • the hydrogenation process is preferably carried out at temperatures of from -80°C to 110°C, more preferably at from -50°C to 90°C and especially at from -40°C to 80°C.
  • the hydrogenation process is preferably carried out at a pressure of from 1 to 100 atmospheres, more preferably at from 1 to 25 atmospheres.
  • the catalyst is preferably present at a concentration of 0.001 to 5.0 mol% of the compound having the double bond, more preferably at from 0.01 to 1.0 mol%.
  • a co-catalyst is preferably used.
  • Preferred co-catalysts are alkali metal aluminium dihydride dialkoxides such as lithium aluminium dihydride di(tertiary butoxide), or an alkali metal hydride such as sodium hydride, or a metal such as sodium or magnesium, or an alkyllithium such as butyllithium, or a Grignard Reagent of formula R'MgX 2 in which R' is alkyl or aryl and X 2 is -Cl, -Br or -I.
  • a preferred co-catalyst is sodium bis(2methoxyethoxy) aluminium hydride.
  • Relative amounts of co-catalyst to catalyst are preferably in a ratio of from 0.1 to 20:1 , more preferably from 1 to 10:1.
  • an activator such as a metal fluoride, preferably an alkali metal, such as potassium, fluoride can be employed.
  • the activator may be employed in an amount equivalent in molar terms to the catalyst or may be employed in a molar excess.
  • the hydrogenation process may take place in the presence of a stabilising reagent.
  • An example of such a reagent is PhSiH 3 .
  • the stabilising reagent may be present in an amount of from equimolar to a fifty-fold molar excess based on the amount of catalyst.
  • a process for the asymmetric hydrosilylation of a compound having a double or triple bond which comprises reacting the compound with a hydrosilylating agent in the presence of a compound of Formula (1).
  • Compounds having a double bond which can be hydrosilylated in the presence of a catalyst of Formula (1) include alkenes, imines, vinylamides, ketones, vinylketones and vinylesters, and particularly alkenes, ketones and imines.
  • Suitable liquid media include alkanes, arenes and ethers.
  • Preferred alkanes include C 5-15 alkanes, and more preferably n-hexane, n-heptane, isomers of octane, cyclohexane or decalin.
  • Preferred arenes include toluene, xylene and mesitylene.
  • Preferred ethers include those having the general formula R x -O-R y , wherein R x and R y each independently represents a C 1-6 alkyl or an aryl group or R x and R y together with the O atom form a 5, 6 or 7 membered saturated ring, and more preferably diethylether, diisopropylether, t-butylmethylether, diphenylether or tetrahydrofuran. It has surprisingly been found that the addition of water, for example at an amount up to 1 equivalent based on the catalyst can increase the enantiomeric excess of one of the isomers of the asymmetric reaction product.
  • the hydrosilylating agent may be a compound known in the art to hydrosilylate double or triple bonds.
  • Preferred hydrosilylating agents include those of the formula R a R b R c SiH, wherein each of R a c independently represents an alkyl, aryl or halo group, or H, provided at least one of R a c represents alkyl, aryl or halo, such as dichlorosilane, Ph 3 SiH, Ph 2 SiH 2 and PhSiH 3 .
  • Other preferred hydrosilylating agents include polymeric silanes, such as poly(methylhydrosiloxane) and poly(phenylhydrosiioxane).
  • the hydrosilylation process can be carried out at temperatures of from -80°C to 110°C, more preferably at from -50°C to 90°C and especially at from -40°C to 80°C.
  • the hydrogenation process is preferably carried out at ambient pressure.
  • the catalyst of Formula (1) is most often present at a concentration of about 0.001 mol% to 5 mol%, preferably from 0.01 mol% to 1 mol%, based on the amount of the compound having the double or triple bond.
  • the amount of catalyst employed can be varied appropriately in situations where the compound being hydrosilylated comprises two or more double bonds which it is desired to hydrosilylate, or where it is desired to hydrosilylate twice at a triple bond.
  • co-catalyst is preferably used.
  • Preferred co-catalysts are alkali metal aluminium dihydride dialkoxides such as lithium aluminium dihydride di(tertiary butoxide), or an alkali metal hydride such as sodium hydride, or a metal such as sodium or magnesium, or an alkyllithium such as butyllithium, or a Grignard Reagent of formula
  • a preferred co-catalyst is sodium bis(2methoxyethoxy) aluminium hydride.
  • Relative amounts of co-catalyst to catalyst are preferably in a ratio of from 0.1 to 20:1 , more preferably from 1 to 10:1.
  • an activator such as a metal fluoride, preferably an alkali metal, such as potassium, fluoride can be employed. The activator may be employed in an amount equivalent in molar terms to the catalyst or may be employed in a molar excess.
  • Toluenesuiphonylchloride (32.7g) was added to a solution of (-)-menthol (25. Og) in pyridine (75 cm 3 ). The mixture was stirred for 46 hours before quenching with ice/water
  • (+)-menthyltosylate (31.7g, 0.1 mol) in THF (100 cm 3 ) via cannula.
  • the mixture was heated under reflux for 6 hours producing a precipitate of sodium tosylate.
  • the mixture was filtered and the solvent removed in vacuo to produce a brown viscous residue which was redissolved in diethyl ether and washed with water (3 x 100 cm 3 ).
  • the organic layer was dried over Na 2 SO 4 , filtered and the solvent removed in vacuo to yield a brown oil which was distilled at reduced pressure to yield the product as a colourless liquid (3.07g, 15%, 95% pure G.C.) b.p.
  • 2,3,4,5-Tetramethylcyclopent-2-enone (18.8g, 0.13 mol in diethyl ether (50 cm 3 ) was added over 1 hour to a suspension of lithium aluminium hydride (2.5g 0.07 mol) in diethyl ether (200 cm 3 ) and the mixture was stirred for a further 2 hours.
  • Aqueous hydrochloric acid (1.0 M, 300 cm 3 ) was added slowly and when the addition was complete the mixture was stirred overnight in air.
  • the organic layer was separated and the aqueous layer washed with diethyl ether (3 x 100 cm 3 ).
  • the ether washings were combined with the organic layer, washed with a saturated sodium carbonate solution (2 x 50 cm 3 ) and dried over Na 2 SO 4 .
  • (+)-Neomenthylcyclopentadienyllithium (3.07g, 0.015 mol) was prepared by the addition of a solution of n-butyllithium (2.5 M, 10.8 cm 3 , 0.27 mol) in hexane to a solution of (+)-neomenthylcyclopentadiene (5.51 g, 0.027 mol) in THF (50 cm 3 ) at 0°C followed by stirring at room temperature for 30 minutes. This solution was transferred at room temperature via cannula to a solution of 1-(chlorodimethylsilyl)-2, 3,4,5- tetramethylcyclopentadiene (4.29g, 0.02 mol) in of THF (50 cm 3 ).
  • Example 5 As for Example 5 except 0.01 mol equiv. of catalyst were used in the reaction heated at 65°C for 18 hours. GC analysis showed that 92% of the acetophenone had been converted to 1-phenylethanol of 82.5% (S) and 17.5% (R).

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Abstract

L'invention concerne des composés organométalliques de formule 1): dans laquelle R?1, R2, R3, et R4¿ représentent indépendamment hydrogène, alkyle, aryle, ou R?1 et R2, ou R2 et R3, ou R3 et R4¿ forment avec les atomes auquels ils sont fixés un cycle à 5 ou 6 éléments; R?5, R6, R7, et R8¿ représentent indépendamment hydrogène, alkyle, aryle, ou forment un groupe de formule -Si(R11)3, -P(R12)2 ou -N(R13)2, R?11, R12, et R13¿ représentant chacun indépendamment alkyle ou aryle, à condition qu'au moins R?5, ou R6, ou R7, ou R8¿ soit un groupe alkyle renfermant 5 atomes de carbone ou plus, ce groupe étant ramifié au niveau de l'atome alpha de carbone à la chaîne cyclopentadiène, ou soit un groupe de formule -Si(R11)3, -P(R12)2 ou -N(R13)2; R?9 et R10¿ représentent indépendamment alkyle ou aryle; M est un métal choisi dans le groupe composé par Ti, Zr, et Hf; n est égal à 2; et X est halo ou aryloxy, ou (X)¿n? peut former avec l'atome de métal auquel il est fixé un cycle à 5, 6, ou 7 éléments. Les composés préférés renferment un groupe menthyle ou néomenthyle. Les composés de formule 1) peuvent être utilisés en tant que catalyseurs, en particulier sous forme optiquement active.
PCT/GB1998/002548 1997-08-28 1998-08-24 Composes organometalliques et leur procede de preparation et d'utilisation WO1999011648A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1671983A1 (fr) * 2004-12-03 2006-06-21 Repsol Quimica S.A. Compositions catalytiques pour le polymérisation et le copolymérisation des alpha-oléfines

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344887A2 (fr) * 1988-03-21 1989-12-06 Exxon Chemical Patents Inc. Composés des métaux transitoirs ponté par un atome de silicium
EP0399348A2 (fr) * 1989-05-20 1990-11-28 Hoechst Aktiengesellschaft Procédé de préparation de polymères d'éthylène
WO1994010180A1 (fr) * 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
US5330948A (en) * 1992-03-31 1994-07-19 Northwestern University Homogeneous catalysts for stereoregular olefin polymerization
EP0610852A1 (fr) * 1993-02-12 1994-08-17 Hoechst Aktiengesellschaft Procédé de préparation de copolymères de cyclo-oléfines
WO1997014727A1 (fr) * 1995-10-19 1997-04-24 Amoco Corporation Systeme de polymerisation homogene d'olefine, a base d'un compose metallocene et a activite accrue
US5631202A (en) * 1993-09-24 1997-05-20 Montell Technology Company B.V. Stereospecific metallocene catalysts with stereolocking α-CP substituents

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344887A2 (fr) * 1988-03-21 1989-12-06 Exxon Chemical Patents Inc. Composés des métaux transitoirs ponté par un atome de silicium
EP0399348A2 (fr) * 1989-05-20 1990-11-28 Hoechst Aktiengesellschaft Procédé de préparation de polymères d'éthylène
US5330948A (en) * 1992-03-31 1994-07-19 Northwestern University Homogeneous catalysts for stereoregular olefin polymerization
WO1994010180A1 (fr) * 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
EP0610852A1 (fr) * 1993-02-12 1994-08-17 Hoechst Aktiengesellschaft Procédé de préparation de copolymères de cyclo-oléfines
US5631202A (en) * 1993-09-24 1997-05-20 Montell Technology Company B.V. Stereospecific metallocene catalysts with stereolocking α-CP substituents
WO1997014727A1 (fr) * 1995-10-19 1997-04-24 Amoco Corporation Systeme de polymerisation homogene d'olefine, a base d'un compose metallocene et a activite accrue

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1671983A1 (fr) * 2004-12-03 2006-06-21 Repsol Quimica S.A. Compositions catalytiques pour le polymérisation et le copolymérisation des alpha-oléfines

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