[EN] BIDENTATE SECONDARY PHOSPHINE OXIDE CHIRAL LIGANDS FOR USE IN ASYMMETRIC ADDITION REACTIONS<br/>[FR] LIGANDS CHIRAUX BIDENTATES LIÉS À UN OXYDE DE PHOSPHINE SECONDAIRE ET LEUR UTILISATION DANS DES RÉACTIONS D'ADDITION ASYMÉTRIQUE
申请人:SOLVIAS AG
公开号:WO2009065783A1
公开(公告)日:2009-05-28
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 C 1-C 4-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-C 4-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 molarratio of ligand to metal of about 1.3:1 to 0.9:1are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.
公式I的化合物以纯对映体形式或以主要含有一种对映体的混合物的形式存在,其中二级膦-Q-P *(= O)HR1(I)中的二级膦是C-键结的二级膦基团-P(R)2;其中R分别是烃基或杂原子烃基;Q是二价的、不手性的、芳香基骨架、二价的、不手性的二茂铁基骨架、可选取代的二价环烷烃或杂环烷烃骨架,或C1-C4-烷基骨架,在这些基骨架中,二级膦基团直接键合到碳原子上,或在环状基骨架的情况下,直接键合到碳原子或通过C1-C4-烷基链键合,其中在这些基骨架中,P-手性基团-P *(O)HR1 键合到碳原子,使得磷原子通过由O、S、N、Fe或Si组成的杂原子随意中断的1到7个碳链原子链接;P *是手性磷原子;R1是烃基、C-键结的杂原子烃基或二茂铁基基团,但当Q是不手性的二茂铁基骨架时,R1是不手性的二茂铁基基团。这些配体的金属配合物在配体与金属的摩尔比约为1.3:1至0.9:1的情况下是对称加成反应的均相催化剂,特别是氢化反应。