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    • 3. 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。
    • 7. 发明申请
    • CHIRAL LIGANDS
    • US20110275826A1
    • 2011-11-10
    • US13141379
    • 2009-12-22
    • Andreas PfaltzMarcus Georg SchremsBenoît Pugin
    • Andreas PfaltzMarcus Georg SchremsBenoît Pugin
    • C07F15/00C07F7/18C07F9/653
    • C07F9/653C07B53/00C07F15/0033
    • Chiral compounds of the formula (1), which are optically pure or highly optically enriched in which R0 is C1-C12-alkyl which is unsubstituted or substituted by 1 to 2 C1-C4-alkoxy; cyclo-pentyl or cyclohexyl, which is unsubstituted or substituted by 1 to 3 C1-C4-alkyl or C1-C4-alkoxy; or benzyl, phenyl or naphtyl which is unsubstituted or substituted by 1 to 3 C1-C4-alkyl, C1-C4-alkoxy, C1-C4-fluoroalkyl or C1-C4-fluoroalkoxy, F or Cl, or R0 is —CR5R6OH or —CR5R6OSi(C1-C8-alkyl)3 wherein R5 and R6 are independently selected from the group consisting of H, unsubstituted C1-C12 alkyl, substituted C1-C12 alkyl, unsubstituted C4-C8 cyclo alkyl, substituted C4-C8 cyclo alkyl, unsubstituted aryl, substituted aryl or wherein R5 and R6 can form an unsubstituted 5-6 membered aliphatic carbocycle or a substituted 5-6 membered aliphatic carbocycle, each of R1 and R′1 independently is hydrogen or has the meaning of R0 whereby R1, R′1 and R0 can be same or different, R2 and R3 are independently a C-bonded hydrocarbon radical or a heterohydrocarbon radical, and each of both R4 is C1-C6-alkyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, methylbenzyl or benzyl, or both R4 together form an aliphatic C4-C6 carbocycle. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reaction, particularly hydrogenations.
    • 式(1)的手性化合物,其是光学纯的或高度光学富集的,其中R 0是未被取代或被1至2个C 1 -C 4 - 烷氧基取代的C 1 -C 12 - 烷基; 环戊基或环己基,其是未取代的或被1至3个C 1 -C 4 - 烷基或C 1 -C 4 - 烷氧基取代; 或未被取代或被1至3个C 1 -C 4 - 烷基,C 1 -C 4 - 烷氧基,C 1 -C 4 - 氟代烷基或C 1 -C 4 - 氟烷氧基,F或Cl或R 10表示的苄基,苯基或萘基是-CR 5 R 6 OH或 - CR5R6OSi(C1-C8-烷基)3,其中R5和R6独立地选自H,未取代的C1-C12烷基,取代的C1-C12烷基,未取代的C4-C8环烷基,取代的C4-C8环烷基,未取代的 芳基,取代的芳基或其中R5和R6可以形成未取代的5-6元脂族碳环或取代的5-6元脂族碳环,R 1和R'1各自独立地是氢或具有R 0的含义,其中R 1,R' 1和R 0可以相同或不同,R2和R3独立地是C键合的烃基或杂烃基,并且R 2各自为C 1 -C 6 - 烷基,环戊基,环己基,苯基,甲基苯基,甲基苄基或苄基,或 R4一起形成脂族C 4 -C 6碳环。 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。