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    • 5. 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。