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    • 2. 发明授权
    • Bidentate secondary phosphine oxide chiral ligands for use in asymmetric addition reactions
    • 用于不对称加成反应的二齿次膦氧化物手性配体
    • US08415488B2
    • 2013-04-09
    • US12734726
    • 2008-11-14
    • Benoît PuginHeidi LandertBjörn GschwendAndreas PfaltzFelix Spindler
    • Benoît PuginHeidi LandertBjörn GschwendAndreas PfaltzFelix Spindler
    • C07D333/62
    • C07F9/65517B01J31/2495B01J2231/643B01J2231/645B01J2531/822B01J2531/827C07B53/00C07B2200/07C07C67/303C07C67/31C07C213/02C07C231/12C07C231/18C07F9/46C07F9/5018C07F9/5022C07F9/655354C07C69/34C07C69/732C07C69/675C07C217/08C07C233/47
    • 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.
    • 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。
    • 4. 发明授权
    • Ferrocene diphosphines as ligands for homogeneous catalysts
    • 二茂铁二膦作为均相催化剂的配体
    • US5563308A
    • 1996-10-08
    • US461349
    • 1995-06-05
    • Felix SpindlerAmina Wirth-TijaniHeidi Landert
    • Felix SpindlerAmina Wirth-TijaniHeidi Landert
    • B01J31/22B01J31/24C07B61/00C07C67/31C07C69/732C07C213/08C07C231/14C07C231/18C07C233/54C07F15/02C07F17/02C07C5/02C07F17/00
    • C07F17/02B01J31/2291B01J31/2295B01J31/2409B01J31/2471C07C213/08C07C231/18C07C67/31B01J2231/643B01J2231/645B01J2531/0205B01J2531/822B01J2531/827B01J2531/842Y10S526/943
    • 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.
    • 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。
    • 9. 发明授权
    • Ferrocene diphosphines as ligands for homogeneous catalysts
    • 二茂铁二膦作为均相催化剂的配体
    • US5466844A
    • 1995-11-14
    • US313484
    • 1994-09-27
    • Felix SpindlerAmina Wirth-TijaniHeidi Landert
    • Felix SpindlerAmina Wirth-TijaniHeidi Landert
    • B01J31/22B01J31/24C07B61/00C07C67/31C07C69/732C07C213/08C07C231/14C07C231/18C07C233/54C07F15/02C07F17/02
    • C07F17/02B01J31/2291B01J31/2295B01J31/2409B01J31/2471C07C213/08C07C231/18C07C67/31B01J2231/643B01J2231/645B01J2531/0205B01J2531/822B01J2531/827B01J2531/842Y10S526/943
    • 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.
    • 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。