Bidentate secondary phosphine oxide chiral ligands for use in asymmetric addition reactions
    1.
    发明授权
    Bidentate secondary phosphine oxide chiral ligands for use in asymmetric addition reactions 失效
    用于不对称加成反应的二齿次膦氧化物手性配体

    公开(公告)号:US08415488B2

    公开(公告)日:2013-04-09

    申请号:US12734726

    申请日:2008-11-14

    IPC分类号: C07D333/62

    摘要: Compounds of the formula I, in the form of mixtures comprising predominantly one enantiomer or in the form of pure enantiomers, secondary phosphine-Q-P*(═O)HR1 (I) in which secondary phosphine is a C-bonded, secondary phosphine group —P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group, and in which base skeletons a P-chiral group —P*(O)HR1 is bonded to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; and R1 is a hydrocarbon radical, a C-bonded heterohydrocarbon radical or a ferrocenyl radical, with the proviso that R1 is an achiral ferrocenyl radical when Q is an achiral ferrocenyl base skeleton. Metal complexes of these ligands in a molar ratio of ligand to metal of about 1.3:1 to 0.9:1 are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

    摘要翻译: 主要以一种对映体或纯对映异构体形式的混合物形式的式I化合物,其中次膦是C键,仲膦基的仲膦-PQ *(= O)HR1(I) P(R)2; 其中R各自独立地为烃基或杂烃基; Q是二价,非手性,芳族碱基骨架,二价,非手性二茂铁碱骨架,任选取代的二价环烷烃或杂环烷骨架,或C 1 -C 4亚烷基骨架,其中碱基骨架的仲膦基直接键合到 碳原子,或者在环状基骨架的情况下,直接与碳原子或C 1 -C 4 - 亚烷基直接键合,并且其中的基础骨架将P手性基团-P *(O)HR1键合到 碳原子,使得磷原子通过1至7个碳链连接,任选被来自O,S,N,Fe或Si基团的杂原子中断; P *是手性磷原子; 并且R 1是烃基,C键合的杂烃基或二茂铁基,条件是当Q是非手性二茂铁基时,R 1是非手性二茂铁基。 配体与金属的摩尔比约为1.3:1至0.9:1的这些配体的金属络合物是用于不对称加成反应,特别是氢化的均相催化剂。

    BIDENTATE CHIRAL LIGANDS FOR USE IN CATALYTIC ASYMMETRIC ADDITION REACTIONS
    2.
    发明申请
    BIDENTATE CHIRAL LIGANDS FOR USE IN CATALYTIC ASYMMETRIC ADDITION REACTIONS 有权
    用于催化不对称添加反应的双歧杆菌配体

    公开(公告)号:US20110118482A1

    公开(公告)日:2011-05-19

    申请号:US12734696

    申请日:2008-11-14

    摘要: Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z1-Q-P*R0R1 (I) in which Z1 is a C-bonded, secondary phosphine group —P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Z1 is the —P*R0R1 group; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group Z1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group, and in which base skeletons a P-chiral group —P*R0R1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; R0 is methyl or hydroxyl, and R0 is methyl when Z1 is the —P*R0R1 group; and R1 is a C-bonded optically enriched or optically pure chiral, mono- or polycyclic, nonaromatic hydrocarbon or heterohydrocarbon radical which has 3 to 12 ring atoms and 1 to 4 rings and which has a stereogenic carbon atom at least in the a position to the P—C bond; Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

    摘要翻译: 主要为一种非对映体或纯非对映体形式的混合物形式的式(I)化合物,其中Z 1为C键,仲膦基-P(R)的Z1-QP * R0R1(I) 2; 其中R各自独立地为烃基或杂烃基,或Z1为-P * R0R1基团; Q是二价,非手性,芳族碱基骨架,二价,非手性二茂铁碱骨架,任选取代的二价环烷烃或杂环烷骨架,或C1-C4-亚烷基骨架,其中,基骨架中的次膦基Z1直接键合 或在环状基团骨架的情况下直接与碳原子或C 1 -C 4 - 亚烷基直接键合,并且其中的基础骨架中,P手性基团-P * R0R1直接键合到碳上 或者在环状基骨架的情况下,直接连接到碳原子上,或者通过C1-C4-亚烷基与碳原子连接,使得磷原子通过1至7个任选被杂原子中断的碳链原子连接 由O,S,N,Fe或Si组成; P *是手性磷原子; R 0是甲基或羟基,当Z 1是-P * R 0 R 1基团时,R 0是甲基; 并且R 1是C-键合的光学富集或光学纯的手性,单或多环,非芳族烃或杂烃基,其具有3至12个环原子和1至4个环,并且其具有立体碳原子至少在 P-C键; 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。

    Ferrocene diphosphines as ligands for homogeneous catalysts
    3.
    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:US5563308A

    公开(公告)日:1996-10-08

    申请号:US461349

    申请日:1995-06-05

    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 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。

    BIDENTATE SECONDARY PHOSPHINE OXIDE CHIRAL LIGANDS FOR USE IN ASYMMETRIC ADDITION REACTIONS
    4.
    发明申请
    BIDENTATE SECONDARY PHOSPHINE OXIDE CHIRAL LIGANDS FOR USE IN ASYMMETRIC ADDITION REACTIONS 失效
    用于非对称添加反应的二次磷酸二氢氧化锡配体

    公开(公告)号:US20110098485A1

    公开(公告)日:2011-04-28

    申请号:US12734726

    申请日:2008-11-14

    摘要: Compounds of the formula I, in the form of mixtures comprising predominantly one enantiomer or in the form of pure enantiomers, secondary phosphine-Q-P*(═O)HR1 (I) in which secondary phosphine is a C-bonded, secondary phosphine group —P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group, and in which base skeletons a P-chiral group —P*(O)HR1 is bonded to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; and R1 is a hydrocarbon radical, a C-bonded heterohydrocarbon radical or a ferrocenyl radical, with the proviso that R1 is an achiral ferrocenyl radical when Q is an achiral ferrocenyl base skeleton. Metal complexes of these ligands in a molar ratio of ligand to metal of about 1.3:1 to 0.9:1 are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

    摘要翻译: 主要以一种对映体或纯对映异构体形式的混合物形式的式I化合物,其中次膦是C键,仲膦基的仲膦-PQ *(= O)HR1(I) P(R)2; 其中R各自独立地为烃基或杂烃基; Q是二价,非手性,芳族碱基骨架,二价,非手性二茂铁碱骨架,任选取代的二价环烷烃或杂环烷骨架,或C 1 -C 4亚烷基骨架,其中碱基骨架的仲膦基直接键合到 碳原子,或者在环状基骨架的情况下,直接与碳原子或C 1 -C 4 - 亚烷基直接键合,并且其中的基础骨架将P手性基团-P *(O)HR1键合到 碳原子,使得磷原子通过1至7个碳链连接,任选被来自O,S,N,Fe或Si基团的杂原子中断; P *是手性磷原子; 并且R 1是烃基,C键合的杂烃基或二茂铁基,条件是当Q是非手性二茂铁基时,R 1是非手性二茂铁基。 配体与金属的摩尔比约为1.3:1至0.9:1的这些配体的金属络合物是用于不对称加成反应,特别是氢化的均相催化剂。

    Functionalized ferrocenyldiphosphines, a process for their preparation and their use
    5.
    发明授权
    Functionalized ferrocenyldiphosphines, a process for their preparation and their use 失效
    官能化的二茂铁二膦,其制备方法及其用途

    公开(公告)号:US06169192A

    公开(公告)日:2001-01-02

    申请号:US09214667

    申请日:1999-01-08

    IPC分类号: C07F1702

    摘要: The invention relates to 1,2-ferrocenyldiphosphines which contain a functional group in the 1′ position either directly or via a bridging group, and also a process for their preparation. The compounds are important for transition metal complexes containing d-8 metals such as Rh, Ru, Pd or Ir. These transition metal complexes are widely used in the hydrogenation of organic double or triple bonds, in particular olefinic double bonds and carbon-heteroatom double bonds. The complexes are particularly suitable for enantioselective hydrogenation using chiral ferrocenyldiphosphines and corresponding prochiral unsaturated compounds. Ferrocenyldiphosphines having a functional group in the 1′ position are also important intermediates for ferrocenyldiphosphine ligands and their metal complexes of d-8 metals such as rhodium, ruthenium, palladium or iridium which are bound to inorganic polymeric supports via this functional group. These metal complexes bound to an inorganic or organic support material are likewise very suitable for the hydrogenation of organic double or triple bonds.

    摘要翻译: 本发明涉及直接或通过桥连基团在1'位置含有官能团的1,2-二茂铁基二膦,以及它们的制备方法。 该化合物对于含有d-8金属如Rh,Ru,Pd或Ir的过渡金属络合物是重要的。 这些过渡金属络合物广泛用于有机双键或三键的氢化,特别是烯属双键和碳 - 杂原子双键。 配合物特别适用于使用手性二茂铁二膦和相应的前手性不饱和化合物的对映选择性氢化。 在1'位置具有官能团的二茂铁基二膦也是二茂铁基二膦配体及其金属络合物的重要中间体,其中d-8金属如铑,钌,钯或铱通过该官能团与无机聚合物载体结合。 与无机或有机载体材料结合的这些金属络合物同样非常适用于有机双键或三键的氢化。

    Ferrocene diphosphines as ligands for homogeneous catalysts
    7.
    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。