Iridium complexes, process for their preparation and their use
    4.
    发明授权
    Iridium complexes, process for their preparation and their use 失效
    IRIDIUM复合物,其制备方法及其使用

    公开(公告)号:US5112999A

    公开(公告)日:1992-05-12

    申请号:US580711

    申请日:1990-09-11

    CPC分类号: C07F15/004

    摘要: Compounds of general formula I or Ia ##STR1## or mixtures thereof, wherein the groups P-L-P are a ligand from the group comprising diphosphine and diphosphinite, in which the secondary phosphine groups or phosphinite groups P are coupled via 2 to 4 C atoms, and which form a 5-, 6- or 7-membered ring with the Ir atoms, X, X.sup.1, X.sup.2, X.sup.3, X.sup.4, X.sup.5 and X.sup.6 independently of the others are Cl, Br or I, or X.sup.1 and X.sup.6 and H and X.sup.2, X.sup.3, X.sup.4 and X.sup.5 independently of the others are Cl, Br or I, or X.sup.1 and X.sup.5 and H and X.sup.2, X.sup.3, X.sup.4 and X.sup.6 independently of the others are Cl, Br or I, and M.sup..sym. is an alkali metal cation or quaternary ammonium. The compounds are suitable as homogeneous catalysts for the (preferably) asymmetric hydrogenation of N-substituted imines to secondary amines.

    摘要翻译: (Ⅰ)或其混合物的通式I或Ia化合物或其混合物,其中基团PLP是来自包括二膦和二磷酸盐的基团的配体,其中仲膦基团或次膦酸基团P连接 通过2至4个C原子,并且与Ir原子形成5-,6-或7-元环,其中X,X 1,X 2,X 3,X 4,X 5和X 6独立地为Cl,Br或I, 或者X 1和X 6以及H和独立地为Cl,Br或I的X 1,X 3,X 4和X 5分别为Cl,Br或I,或者X 1和X 5以及H和独立地为Cl,Br或I的X 2,X 3,X 4和X 6, M(+)是碱金属阳离子或季铵。 该化合物适合用作(优选)N-取代亚胺对仲胺的不对称氢化的均相催化剂。

    Diphosphine ligands
    5.
    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
    6.
    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。

    Process for the preparation of (R)-2-alkyl-3-phenyl-1-propanols
    7.
    发明授权
    Process for the preparation of (R)-2-alkyl-3-phenyl-1-propanols 失效
    制备(R)-2-烷基-3-苯基-1-丙醇的方法

    公开(公告)号:US06881868B2

    公开(公告)日:2005-04-19

    申请号:US10312992

    申请日:2001-06-26

    摘要: Compounds of formula (I), wherein R1 and R2 are, independently of one another, H,C1-C6alkyl, C1-C6halogenalkyl, C1-C6alkoxyl, C1-C6alkoxy-C1-C6alkyl, or C1-C6alkoxy-C1-C6alkyloxy, and R3 is C1-C6alkyl, are obtainable in high yiedls by stereoselective addition of R3-substituted propionic acid esters to R1- and R2-substituted benzaldehydes of formula R—CHO to form corresponding 3-R-3-hydroxy-2-R3-propionic acid esters, conversion of the OH group to a leaving group, subsequent regioselective elimination to form 3-R-2-R3-propenic acid esters, and reduction to corresponding 3-R-2-R3-allyl alcohols and their enantioselective hydrogenation, wherein R is (a).

    摘要翻译: 式(I)化合物,其中R 1和R 2各自独立地为H,C 1 -C 3烷基, C 1 -C 6烷基,C 1 -C 6卤代烷基,C 1 -C 6烷氧基,C C 1 -C 6烷氧基-C 1 -C 6烷基或C 1 -C 12 -C 6 -C 6烷氧基-C 1 -C 6烷氧基,R 3是C 1 可以通过立体选择性加成R 3 - 取代的丙酸酯与R 1 - (C 1 -C 6)烷基取代, 和R 2 CHO的R 2取代的苯甲醛形成相应的3-R-3-羟基-2-R 3 - 丙酸酯,OH基团的转化 到离去基团,随后进行区域选择性消除以形成3-R-2-R 3 - 丙酸酯,并还原成相应的3-R-2-R 3 - 烯丙醇及其对映选择性氢化,其中R为(a)。

    Fluoroalkyl-substituted ferrocenyl diphosphines as ligands for
homogeneous catalysts
    9.
    发明授权
    Fluoroalkyl-substituted ferrocenyl diphosphines as ligands for homogeneous catalysts 失效
    氟烷基取代的二茂铁基二膦作为均相催化剂的配体

    公开(公告)号:US5583241A

    公开(公告)日:1996-12-10

    申请号:US313485

    申请日:1994-09-27

    申请人: Felix Spindler

    发明人: Felix Spindler

    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 is a radical of formula II ##STR2## wherein R.sub.12 is C.sub.1 -C.sub.5 alkyl which is partially or completely fluorinated;R.sub.13 is 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 or --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ;m is an integer from 1 to 3, n is 0 or an integer from 1 to 4, and the sum of m+n is 1 to 5;R.sub.3, R.sub.10, R.sub.11 have each independently of one another the same meaning as R.sub.2 or are each independently of one another C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, 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. ;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 or phenyl orR.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; R2是式II的基团(II)其中R12是部分或完全氟化的C 1 -C 5烷基; R13是C1-C4烷基,C1-C4烷氧基,-SiR4R5R6,卤素,-SO3M,CO2M,-PO3M,-NR7R8或 - [(+)NR7R8R9] X( - ); m为1〜3的整数,n为0或1〜4的整数,m + n的和为1〜5。 R 3,R 10,R 11各自独立地为与R 2相同的含义或彼此独立地彼此独立地为C 1 -C 12烷基,C 5 -C 12环烷基,苯基,C 1 -C 4烷基 - 或C 1 -C 4烷氧基取代的C 5 -C 12环烷基或 被一至三个相同或不同的选自C1-C4烷基,C1-C4烷氧基,-SiR4R5R6,卤素,-SO3M,-CO2M,-PO3M,-NR7R8和 - [(+)NR7R8R9] X( - ); R4,R5和R6各自独立地为C1-C12烷基或苯基; R 7和R 8是H,C 1 -C 12烷基或苯基或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或非对映异构体混合物形式的立体碳原子。 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。

    Ferrocene diphosphines as ligands for homogeneous catalysts
    10.
    发明授权
    Ferrocene diphosphines as ligands for homogeneous catalysts 失效
    二茂铁二膦作为均相催化剂的配体

    公开(公告)号:US5466844A

    公开(公告)日:1995-11-14

    申请号:US313484

    申请日:1994-09-27

    摘要: Compounds 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 each independently of the other typically C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, 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 or halogen; R.sub.10 and R.sub.11 are identical and are typically 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 or phenyl which is substituted by 1 to 3 identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen; or R.sub.10 and R.sub.11 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 1 to 3 identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen, and * denotes 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烷氧基取代的苯基; R 2和R 3各自独立地为其它通常为C 1 -C 12烷基,C 5 -C 12环烷基,苯基或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 由C 1 -C 4烷基,C 1 -C 4烷氧基或卤素组成的基团; R 10和R 11是相同的,并且通常是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环烷基或被1至3个相同或不同的选自C1- C4烷基,C1-C4烷氧基或卤素; 或R 10和R 11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,苯基或苯基,其被1至3个相同或不同的选自以下的基团取代: C1-C4烷基,C1-C4烷氧基或卤素,和*表示立体异构碳原子,以其外消旋体和非对映异构体的形式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。