1,1'-Diphosphinoferrocenes Having 2,2'-Bound Achiral Or Chiral Radicals
    53.
    发明申请
    1,1'-Diphosphinoferrocenes Having 2,2'-Bound Achiral Or Chiral Radicals 审中-公开
    具有2,2'-Bound手性或手性基团的1,1'-二膦基二茂铁

    公开(公告)号:US20080026933A1

    公开(公告)日:2008-01-31

    申请号:US11631608

    申请日:2005-07-04

    CPC分类号: C07F17/02

    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.

    摘要翻译: 在式(I)的二茂铁二膦中,其中R表示例如甲基或苯基,在许多情况下,相应的金属络合物的催化性能可以明显受到一个或两个CP环上的结构变化的影响, 可以优化并显着改善对所选择的基材的催化反应。 这种二膦配体可以通过使用新的生产方法获得。

    Ferrocenyl diphosphines and their use
    55.
    发明授权
    Ferrocenyl diphosphines and their use 有权
    二茂铁二膦及其用途

    公开(公告)号:US06777567B2

    公开(公告)日:2004-08-17

    申请号:US10312816

    申请日:2002-12-31

    IPC分类号: C07F1702

    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.

    摘要翻译: 式(I)和(Ia)化合物为外消旋体形式,非对映异构体混合物或基本上为对映体纯形式的(I),(Ia),其中R为氢,C 1 -C 8烷基,C 5 -C 12环烷基,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; n为0或1〜4的整数,R 1为相同或不同的选自C1-C4烷基,C1-C4氟烷基和C1-C4烷氧基的取代基。 X1和X2各自独立地为次膦基; T是C 6 -C 20亚芳基或C 3 -C 16亚芳基; 并且X2相对于T环戊二烯基键在邻位结合。 这些化合物是选自元素周期表的转变基团(I)和(VIII)的金属络合物的配体,这些金属络合物是用于将氢,硼氢化物或硅烷不对称加成到碳 - 碳上的有价值的催化剂 前手性有机化合物中的碳 - 杂原子多重键或碳亲核试剂或胺不对称加成到烯丙基化合物上。

    Ferrocenyl diphosphines as ligands for homogeneous catalysts
    56.
    发明授权
    Ferrocenyl diphosphines as ligands for homogeneous catalysts 失效
    二茂铁基二膦作为均相催化剂的配体

    公开(公告)号:US5563309A

    公开(公告)日:1996-10-08

    申请号:US459435

    申请日:1995-06-02

    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。

    Ferrocenyl diphosphines as ligands for homogeneous catalysts
    57.
    发明授权
    Ferrocenyl diphosphines as ligands for homogeneous catalysts 失效
    二茂铁基二膦作为均相催化剂的配体

    公开(公告)号:US5463097A

    公开(公告)日:1995-10-31

    申请号:US292150

    申请日:1994-08-17

    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。

    Ferrocenyl diphosphines as ligands for homogeneous catalysts
    58.
    发明授权
    Ferrocenyl diphosphines as ligands for homogeneous catalysts 失效
    二茂铁基二膦作为均相催化剂的配体

    公开(公告)号:US5371256A

    公开(公告)日:1994-12-06

    申请号:US037783

    申请日:1993-03-26

    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。

    Diphosphines containing silane groups, immobilized diphosphines and the
use thereof as hydrogenation catalysts
    60.
    发明授权
    Diphosphines containing silane groups, immobilized diphosphines and the use thereof as hydrogenation catalysts 失效
    含有硅烷基团的二膦,固定化二膦及其作为氢化催化剂的用途

    公开(公告)号:US5306853A

    公开(公告)日:1994-04-26

    申请号:US78696

    申请日:1993-06-17

    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.

    摘要翻译: 式(II)化合物其中基团(R 1)2 P(CH 2)m bzw.n彼此是邻位或间位,取代基R 1是相同或不同的基团,m和n各自为 独立于另一个0或1,R 1是被C 1 -C 4烷基或C 1 -C 4烷氧基取代的直链或支链C 1 -C 12烷基,未被取代的C 5 -C 6环烷基或C 5 -C 6环烷基,或者是苯基或苄基,或两个基团中的两个取代基R 1 (R1)2P一起为o,邻二亚苯基,-R2-X-为键或 - (CxH2x-O)y-或X-为O-,R2为C1-C6亚烷基,x为2的整数 至6,y为2至6的整数,R 3为C 2 -C 18亚烷基,亚苯基或亚苯基,且R 4为C 1 -C 6烷基或苯基,可用于固体载体如硅胶或气溶胶,并与铑或 铱化合物。 这些材料是用于不对称氢化含有双键或碳/杂原子双键的前手性化合物的非均相和可分离的催化剂,例如酮和亚胺。