摘要:
Diphosphines of a mixed heteroarylic-arylic type, wherein the phosphine group carrying backbone is constituted by the interconnection of a five-atom heteroaromatic ring and a carbocyclic aromatic ring, forming an atropoisomeric chiral system with a C.sub.1 symmetry. Said chiral diphosphines are advantageously used as ligands for the formation of chiral complexes with transition metals, in particular Ru, Rh, Pd, Ir, Ni. The so-obtained chiral complexes are used as chiral complexes are used as chiral catalysts for stereocontrolled reactions, in particular diastereo and enantioselective reduction reactions, hydroformylation reactions, hydrosilylation reactions, hydrocyanation reactions, double-bond isomerisation reactions, other reactions of carbon--carbon bond formation.
摘要:
BIDENTATE COORDINATES OF THE FORMULA R2X-R''-YR2, IN WHICH X AND Y ARE PHOSPHORUS, ARSENIC, ANTIMONY OR NITROGEN, R'' IS A HYDROCARBON GROUP CONTAINING AN ASYMMETRIC CARBON ATOM AND THE R GROUPS ARE HYDROCARBON RADICALS, MAY BE ASSOCIATED WITH RHODIUM COMPLEXES TO YIELD HYDROGENATION CATALYSTS USEFUL IN ASYMMETRIC SYNTHESIS. THE SYNTHESIS OF OPTICALLY ACTIVE AMINOACIDS OR AMINES IS CONCERNED.
摘要:
Compounds of the formula (I) or (I′), where R1 is a hydrogen atom or C1-C4-alkyl and R′1 is C1-C4-alkyl; X1 and X2 are each, independently of one another, a secondary phosphine group; R2 is hydrogen, R01R02R03Si—, C1-C18.acyl substituted by halogen, hydroxy, C1-C8-alkoxy or R04R05N—, -or R06—X01—C(O)—; R01, R02 and R03 are each, independently of one another, C1-C12-alkyl, unsubstituted or C1-C4-alkyl or C1-C4-alkoxy-substituted C6-C10-aryl or C7-C12-aralkyl; R04 and R05 are each, independently of one another, hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, C6-C10-aryl or C7-C12-aralkyl, or R04 and R05 together are trimethylene, tetramethylene, pentamethylene or 3-oxapcntylene; R06 is C1-C18-alkyl, unsubstituted or C1-C4-alkyl- or C1-C4-alkoxy-substituted C3-C8-cycloalkyl, C6-C10-aryl or C7-C12-aralkyl; X01 is —O— or —NH—; T is C6-C20-arylene; v is 0 or an integer from 1 to 4; and * denotes a mixture of racemic or enantiomerically pure diastereomers or pure racemic or enantiomerically diastereomers, are excellent chiral ligands for metal complexes as enantioselective catalysts for the hydrogenation of prochiral organic compounds.
摘要:
Compounds of formula I wherein R1 is C1-C8alkyl, phenyl or phenyl which is substituted by 1 to 3 C1-C4alkyl or C1-C4alkoxy groups; R2 and R3 are identical and are C1-C12alkyl, C5-C12cycloalkyl or C1-C4alkyl- or C1-C4alkoxy-substituted C5-C12cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C1-C4alkyl, C1-C4alkoxy, —SiR4R5R6, halogen, —SO3M, —CO2M, —PO3M, —NR7R8 and —[⊕NR7R8R9]X⊖; or R2 and R3 are different and are C1-C12alkyl, C5-C12cycloalkyl, C1-C4alkyl- or C1-C4-alkoxy-substituted C5-C12cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C1-C4alkyl, C1-C4alkoxy, —SiR4R5R6, halogen, —SO3M, —CO2M, —PO3M2, —NR7R8 and —[⊕NR7R8R9]X⊖; or the group —PR2R3 is a radical of formula II and R4, R5 and R6 are each independently of one another C1-C12alkyl or phenyl, R7 and R8 are H, C1-C2alkyl, phenyl or R7 and R8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R9 is H or C1-C4alkyl, M is H or an alkali metal, X⊖ is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereomers or mixtures of diastereoisomers. Rhodium and iridium complexes with these ligands are suitable for use as homogeneous enantioselective catalysts for the hydrogenation of prochiral compounds, containing carbon double bonds or carbon/hetero atom double bonds.
摘要:
Optically active piperazine-2-carboxylic acid derivatives of the general formula: ##STR1## wherein R.sup.1 and R.sup.2 are inter alia hydrogen, alkyl or acyl and X is alkoxy or a (substituted) amino group, are prepared by asymmetric hydrogenation of the corresponding 1,4,5,6-tetrahydropyrazines, catalyzed by optically active rhodium, ruthenium or iridium complexes. The compounds of the Formula 1 are intermediates for the preparation of pharmaceutical active ingredients, for example, HIV protease inhibitors.
摘要:
Multinuclear catalyst complex comprising two or more active metal centers and at least one phenoxyimine derivative and at least one substituted cyclopentadienyl, indenyl or fluorenyl derivative, each phenoxyimine derivative being bonded to a cyclopentadienyl, indenyl or fluorenyl derivative forming a ligand framework, the cyclopentadienyl, indenyl or fluorenyl derivative being coordinated with one of the metal centers and the phenoxyimine derivative being coordinated with an active metal center other than the metal center the cyclopentadienyl, indenyl or fluorenyl derivative is coordinated with, and wherein the phenoxyimine derivative is derived from a phenoxyimine compound of the formula wherein R1 is hydrogen, alkyl, cycloalkyl, aryl or aralkyl; R2 is hydrogen, halogen, alkyl, cycloalkyl, aryl, O-alkyl or aralkyl; and R3 is alkyl, cycloalkyl, aryl or aralkyl, process for preparing a multinuclear catalyst composition comprising the steps of bonding the substituted phenoxyimine compound to a substituted cyclopentadienyl, indenyl or fluorenyl derivative to obtain a ligand framework and reacting at least one ligand framework with an active metal component and process for the polymerization of olefins, in particular of ethylene and optionally one or more other a-olefins, wherein said multinuclear catalyst is applied.
摘要:
The present invention relates to a process for the efficient preparation of enantiomerically enriched beta amino acid derivatives which are useful in the asymmetric synthesis of biologically active molecules. The process comprises an enantioselective hydrogenation of a prochiral beta amino acrylic acid derivative substrate in the presence of a transition metal precursor complexed with a chiral ferrocenyl diphosphine ligand.
摘要:
Compounds of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are identical and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy,--SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M,--CO.sub.2 M,--PO.sub.3 M,--NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or R.sub.1 and R.sub.3 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy,--SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M,--CO.sub.2 M,--PO.sub.3 M.sub.2, --NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or the group --PR.sub.2 R.sub.3 is a radical of formula II ##STR2## and R.sub.4, R.sub.5 and R.sub.6 are each independently of one another C.sub.1 -C.sub.12 alkyl or phenyl, R.sub.7 and R.sub.8 are H, C.sub.1 -C.sub.12 alkyl, phenyl or R.sub.7 and R.sub.8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R.sub.9 is H or C.sub.1 -C.sub.4 alkyl, M is H or an alkali metal, X.sup..crclbar. is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereoisomers or mixtures of diastereoisomers. Rhodium and iridium complexes with these ligands are suitable for use as homogeneous enantioselective catalysts for the hydrogenation of prochiral compounds containing carbon double bonds or carbon/hereto atom double bonds.
摘要翻译:式I的化合物其中R 1是C 1 -C 8烷基,苯基或被1至3个C 1 -C 4烷基或C 1 -C 4烷氧基取代的苯基; R 2和R 3相同,为C 1 -C 12烷基,C 5 -C 12环烷基或C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基或被一至三个相同或不同的选自C1- C 1-4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或R 1和R 3不同,为C 1 -C 12烷基,C 5 -C 12环烷基,C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基,苯基或被一至三个相同或不同的成员取代的苯基, C 1 -C 4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M 2,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或基团-PR 2 R 3是式II的基团(II),且R 4,R 5和R 6彼此独立地为C 1 -C 12烷基或苯基,R 7和R 8为H,C 1 -C 12烷基,苯基或R 7和R 8 一起是四亚甲基,五亚甲基或3-氧杂-1,5-亚戊基,R9是H或C1-C4烷基,M是H或碱金属,X( - )是一元酸的阴离子,*是 其外消旋体和非对映异构体形式的立体碳原子或非对映异构体的混合物。 与这些配位体的铑和铱络合物适合用作含碳双键或碳/原子双键的前手性化合物氢化的均匀对映选择性催化剂。
摘要:
A complex of the formula V or VI,[X.sub.1 M.sub.1 YZ]X.sub.1 M.sub.1 Y].sup..sym. A.sub.1.sup..crclbar.wherein X.sub.1 is two C.sub.2 -C.sub.12 olefins or one C.sub.5 -C.sub.12 diene, Z is Cl, Br or I, A.sub.1.sup..crclbar. is the anion of an oxyacid or complex acid, M.sub.1 is Rh or Ir, and Y is a compound of the formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are identical and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M, --NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or R.sub.2 and R.sub.3 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M.sub.2, --NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or the group --PR.sub.2 R.sub.3 is a radical of formula II ##STR2## and R.sub.4, R.sub.5 and R.sub.6 are each independently of one another C.sub.1 -C.sub.12 alkyl or phenyl, R.sub.7 and R.sub.8 are H, C.sub.1 -C.sub.12 alkyl, phenyl or R.sub.7 and R.sub.8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R.sub.9 is H or C.sub.1 -C.sub.4 alkyl, M is H or an alkali metal, X.sup..crclbar. is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereoisomers or mixtures of diastereoisomers.
摘要翻译:式Ⅴ或Ⅵ的络合物[X1M1YZ] X1M1Y](+)A1( - )其中X1是两个C2-C12烯烃或一个C5-C12二烯,Z是Cl,Br或I,A1( - )是 含氧酸或络合酸,M1为Rh或Ir,Y为式Ⅰ化合物其中R 1为C 1 -C 8烷基,苯基或被1至3个C 1 -C 4烷基或C 1 -C 4烷基取代的苯基, C4烷氧基; R 2和R 3相同,为C 1 -C 12烷基,C 5 -C 12环烷基或C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基或被一至三个相同或不同的选自C1- C 1-4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或R 2和R 3不同,为C 1 -C 12烷基,C 5 -C 12环烷基,C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基,被一至三个相同或不同的成员所取代的苯基或苯基,所述相同或不同的成员选自 C 1 -C 4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M 2,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或基团-PR 2 R 3是式II的基团(II),且R 4,R 5和R 6彼此独立地为C 1 -C 12烷基或苯基,R 7和R 8为H,C 1 -C 12烷基,苯基或R 7和R 8 一起是四亚甲基,五亚甲基或3-氧杂-1,5-亚戊基,R9是H或C1-C4烷基,M是H或碱金属,X( - )是一元酸的阴离子,*是 其外消旋体和非对映异构体形式的立体碳原子或非对映异构体的混合物。
摘要:
Compounds of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are identical and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M,--NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or R.sub.2 and R.sub.3 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M.sub.2, --NR.sub.7 R.sub.8 and --[.sup..sym.NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or the group --PR.sub.2 R.sub.3 is a radical of formula II ##STR2## and R.sub.4, R.sub.5 and R.sub.6 are each independently of one another C.sub.1 -C.sub.12 alkyl or phenyl, R.sub.7 and R.sub.8 are H, C.sub.1 -C.sub.2 alkyl, phenyl or R.sub.7 and R.sub.8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R.sub.9 is H or C.sub.1 -C.sub.4 alkyl, M is H or an alkali metal, X.sup..crclbar. is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereoisomers or mixtures of diastereoisomers. Rhodium and iridium complexes with these ligands are suitable for use as homogeneous enantioselective catalysts for the hydrogenation of prochiral compounds containing carbon double bonds or carbon/hetero atom double bonds.
摘要翻译:式I的化合物其中R 1是C 1 -C 8烷基,苯基或被1至3个C 1 -C 4烷基或C 1 -C 4烷氧基取代的苯基; R 2和R 3相同,为C 1 -C 12烷基,C 5 -C 12环烷基或C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基或被一至三个相同或不同的选自C1- C 1-4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或R 2和R 3不同,为C 1 -C 12烷基,C 5 -C 12环烷基,C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基,被一至三个相同或不同的成员所取代的苯基或苯基,所述相同或不同的成员选自 C 1 -C 4烷基,C 1 -C 4烷氧基,-SiR 4 R 5 R 6,卤素,-SO 3 M,-CO 2 M,-PO 3 M 2,-NR 7 R 8和 - [(+)NR 7 R 8 R 9] X( - )。 或基团-PR 2 R 3是式II的基团(II),且R 4,R 5和R 6彼此独立地为C 1 -C 12烷基或苯基,R 7和R 8为H,C 1 -C 2烷基,苯基或R 7和R 8 一起是四亚甲基,五亚甲基或3-氧杂-1,5-亚戊基,R9是H或C1-C4烷基,M是H或碱金属,X( - )是一元酸的阴离子,*是 其外消旋体和非对映异构体形式的立体碳原子或非对映异构体的混合物。 与这些配体的铑和铱配合物适合用作含碳双键或碳/杂原子双键的前手性化合物氢化的均匀对映选择性催化剂。