摘要:
Compounds of the formula II can be hydrogenated to the corresponding butane derivatives in the presence of homogeneous cataslysts composed of metal salts or complexes containing metals selected from the group consisting of Rh, Ir, and Ru and preferably containing diphosphine ligands, with, in addition, excellent optical yields being achieved when one of R2 and R3 is not a hydrogen atom and the diphosphine ligand is chiral.
摘要:
In ferrocene diphosphines of formula (I), in which R represents, for example, methyl or phenyl, the catalytic properties of corresponding metal complexes can, in many instances, be distinctly influenced by structural changes on one or both of the CP rings, and the catalytic reaction with regard to selected substrates can be optimized and significantly improved. Diphosphine ligands of this type are accessible by using novel production methods.
摘要:
A process for the hydrogenation of imines with hydrogen under elevated pressure in the presence of iridium catalysts and with or without an inert solvent, wherein the reaction mixture contains an ammonium or metal chloride, bromide or iodide and additionally an acid.
摘要:
Compounds of the formula (I) and (Ia) in the form of racemates, mixtures of diastereomers or in essentially enantiomerically pure form, (I), (Ia), where R is hydrogen, C1-C8alkyl, C5-C12cycloakyl, phenyl or phenyl substituted by from 1 to 3 C1-C4alky or C1-C4alkoxy groups; n is 0 or an integer from 1 to 4 and R1 are identical or different substituents selected from the group consisting of C1-C4alkyl, C1-C4fluoroalkyl and C1-C4alkoxy; X1 and X2 are each, independently of one another, secondary phosphino; T is C6-C20arylene or C3-C16heteroarylene; and X2 is bound in the ortho position relative to the T-cyclopentadienyl bond. The compounds are ligands for complexes of metal selected from transition groups (I) and (VIII) of the Periodic Table of the Elements, and these metal complexes are valuable catalysts for the asymmetric addition of hydrogen, boron hydrides or silanes onto carbon-carbon or carbon-heteroatom multiple bonds in prochiral organic compounds or the asymmetric addition of carbon nucleophiles or amines onto allyl compounds.
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。
摘要:
Compounds where a solid carrier material which contains diphosphine rhodium or iridium complexes fixed on the surface thereof, of which the carrier material has the formula IV or IVa: ##STR1## wherein Y denotes two monoolefin ligands or a diene ligand, M is Ir(I) or Rh(i), Z is --Cl, --Br or -I, A.crclbar. is the anion of an oxyacid or complex acid, T is a solid carrier material, r is 0, 1 or 2, and R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are as defined in claim 1. These materials are heterogeneous and separable catalysts for the asymmetrical hydrogenation of prochiral compounds containing carbon double bonds or carbon/hetero atom double bonds, for example ketones and imines.
摘要:
Compounds of formula II ##STR1## wherein the groups (R.sub.1).sub.2 P(CH.sub.2).sub.m bzw.n are in o- or m-position to each other and the substituents R.sub.1 are identical or different radicals, m and n are each independently of the other 0 or 1, R.sub.1 is linear or branched C.sub.1 -C.sub.12 alkyl, unsubstituted C.sub.5 -C.sub.6 cycloalkyl or C.sub.5 -C.sub.6 cycloalkyl which is substituted by C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, or is phenyl or benzyl, or both substituents R.sub.1 in a group (R.sub.1).sub.2 P together are o,o'-diphenylene, --R.sub.2 --X-- is a bond or --(C.sub.x H.sub.2x --O).sub.y --, or X-- is O-- and R.sub.2 is C.sub.1 -C.sub.6 alkylene, x is an integer from 2 to 6 and y is an integer from 2 to 6, R.sub.3 is C.sub.2 -C.sub.18 alkylene, phenylene or benzylene, and R.sub.4 is C.sub.1 -C.sub.6 alkyl or phenyl, can be applied to solid carriers, such as silica gel or aerosils, and complexed with rhodium or iridium compounds. These materials are heterogeneous and separable catalysts for the asymmetrical hydrogenation of prochiral compounds containing carbon double bonds or carbon/hetero atom double bonds, for example ketones and imines.