Diphosphines containing silane groups, immobilise diphosphines and the
use thereof as hydrogenation catalysts
    4.
    发明授权
    Diphosphines containing silane groups, immobilise diphosphines and the use thereof as hydrogenation catalysts 失效
    含有硅烷基团的二羟基磷灰石,硫化二磷酸酯及其作为氢化催化剂的用途

    公开(公告)号:US5244857A

    公开(公告)日:1993-09-14

    申请号:US823517

    申请日:1992-01-21

    摘要: Compounds of formula II ##STR1## wherein the groups (R.sub.1).sub.2 P(CH.sub.2).sub.m and 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和n彼此相邻或相邻位置,并且取代基R 1是相同或不同的基团,m和n各自独立地为 的另一个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,未取代的C 5 -C 6环烷基或C 5 -C 6环烷基,或是苯基或苄基,或两个取代基R 1 R1)2P一起是o,o'-二亚苯基,-R 2 -X-是键或 - (C x H 2 O-O)y - ,或X是O-,R 2是C 1 -C 6亚烷基,x是从2到 6,y为2〜6的整数,R3为C2-C18亚烷基,亚苯基或亚苯基,R4为C1-C6烷基或苯基,可用于固体载体如硅胶或气溶胶,并与铑或铱络合 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。

    Diphosphines containing silane groups, immobilized diphosphines and the
use thereof as hydrogenation catalysts
    6.
    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。

    Diphosphine ligands
    8.
    发明申请
    Diphosphine ligands 审中-公开
    二膦配体

    公开(公告)号:US20100029967A1

    公开(公告)日:2010-02-04

    申请号:US12308941

    申请日:2007-06-29

    IPC分类号: C07F15/00

    摘要: Compounds of the formulae I and Ia in the form of mixtures of diastereomers or pure diastereomers, (I), (Ia), 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 sec-phosphino group; T is C6-C20-arylene or C4-C18-heteroarylene having heteroatoms selected from the group consisting of O, S, —N═ and N(C1-C4-alkyl); v is 0 or an integer from 1 to 4; X1 is bound in the ortho position relative to the T-C* bond; Q is vinyl, methyl, ethyl, —CH2—OR, —CH2—N(C1-C4-alkyl)2 or a C- or S-bonded chiral group which directs metals of metallation reagents into the ortho position; R is hydrogen, a silyl radical or an aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic hydrocarbon radical which has from 1 to 18 carbon atoms and is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, F or CF3; are ligands for metal complexes as homogeneous catalyst in asymmetric syntheses.

    摘要翻译: 式(I),(Ia),其中R 1是氢原子或C 1 -C 4 - 烷基和R 11是C 1 -C 4 - 烷基的非对映异构体或纯非对映体混合物形式的式I和Ia化合物; X1和X2各自独立地为仲膦基; T是具有选自O,S,-N-和N(C 1 -C 4 - 烷基)的杂原子的C 6 -C 20亚芳基或C 4 -C 18亚杂芳基; v为0或1至4的整数; X1相对于T-C *键的邻位结合; Q是乙烯基,甲基,乙基,-CH 2 -OR,-CH 2 -N(C 1 -C 4烷基)2或C-或S-键合的手性基团,其将金属化试剂的金属引导到邻位; R是氢,具有1至18个碳原子且未被取代或被C 1 -C 4 - 烷基,C 1 -C 4 - 烷氧基,F或CF 3取代的甲硅烷基或脂族,脂环族,芳族或芳族 - 脂族烃基; 是不对称合成中金属络合物作为均相催化剂的配体。

    Ferrocene-Diphosphine Ligands
    9.
    发明申请
    Ferrocene-Diphosphine Ligands 审中-公开
    二茂铁 - 二膦配体

    公开(公告)号:US20090156851A1

    公开(公告)日:2009-06-18

    申请号:US11990208

    申请日:2006-08-10

    IPC分类号: C07F9/02 C07F15/02

    CPC分类号: C07F17/02

    摘要: Compounds of the formula (I) in the form of racemates, mixtures of stereoisomers or optically pure stereoisomers, formula (I), where X1 and X2 are each, independently of one another, a secondary phosphino group; R1 is a halogen atom or a—substituent bound via a C atom, N atom, S atom, Si atom, a P(O) group or a P(S) group to the cyclopentadienyl ring; R2 is C1-C4-alkyl or phenyl; m is from 1 to 3 and n is 0 or from 1 to 5, are ligands for complexes of transition metals as enantioselective and homogeneous catalysts. As a result of the substitution, the conversion, the stereoselectivity and/or the configuration of the adduct formed can be influenced and optimization of catalysts can be made possible in this way.

    摘要翻译: 式(I)化合物为外消旋体形式,立体异构体混合物或光学纯立体异构体式(I),其中X1和X2各自独立地为次膦基; R1是通过C原子,N原子,S原子,Si原子,P(O)基团或P(S)键连接到环戊二烯基环上的卤素原子或取代基; R2是C1-C4烷基或苯基; m为1至3,n为0或1至5为过渡金属络合物作为对映选择性和均相催化剂的配体。 作为取代的结果,可以影响形成的加合物的转化率,立体选择性和/或构型,并且可以以这种方式使催化剂的优化成为可能。

    Chiral Ligands Used in Transition Metal Catysts for Asymmetric Addition Reactions Especially Hydrogenation
    10.
    发明申请
    Chiral Ligands Used in Transition Metal Catysts for Asymmetric Addition Reactions Especially Hydrogenation 有权
    用于非对称加成反应的过渡金属催化剂中的手性配体特别是氢化

    公开(公告)号:US20090171114A1

    公开(公告)日:2009-07-02

    申请号:US12227574

    申请日:2007-05-23

    摘要: Ligands of the formula (I) secondary phosphine-Q-P(═O)HR1 (I) in the form of mixtures of diastereomers or pure diastereomers, in which secondary phosphine is a secondary phosphine group with hydrocarbon radicals or heterohydrocarbon radicals as substituents; Q is a bivalent bisaryl or bisheteroaryl radical with an axial chiral centre to which the two phosphorus atoms are bonded in the ortho positions to the bisaryl or bisheteroaryl bridge bond, or Q is a bivalent ferrocenyl radical with a planar chiral centre or without a planar chiral centre, to which the phosphorus atom of the secondary phosphine is bonded directly or via a C1-C4-carbon chain to a cyclopentadienyl ring, the —P*(═O)HR1 group is bonded either on the same cyclopentadienyl ring in ortho position to the bonded secondary phosphine or on the other cyclopentadienyl ring; P* is a chiral phosphorus atom, and R1 is a hydrocarbon radical, a heterohydrocarbon radical or a ferrocenyl radical, where R1 is a ferrocenyl radical with a planar chiral centre when Q is a ferrocenyl radical without a planar chiral centre. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

    摘要翻译: 式(I)以非对映异构体或纯非对映异构体混合物形式的仲膦-Q-P(-O)HR1(I)的配体,其中次膦是具有烃基或杂烃基作为取代基的仲膦基; Q是具有轴向手性中心的二价双芳基或双杂芳基,其中两个磷原子与双芳基或双杂芳基桥键的邻位键合,或Q是具有平面手性中心或不具有平面手性的二价二茂铁基 中心,仲膦的磷原子直接或通过C1-C4-碳键连接到环戊二烯基环上,-P *( - O)HR 1基团在邻位相邻的环戊二烯基环上键合到 键合的次膦或在另一个环戊二烯基环上; P *是手性磷原子,R1是烃基,杂烃基或二茂铁基,其中当Q是没有平面手性中心的二茂铁基时,R 1是具有平面手性中心的二茂铁基。 这些配体的金属络合物是用于不对称加成反应的均相催化剂,特别是氢化。