轴手性联苯二膦配体的制备及其在不对称氢化反应中的应用。

Preparation of axially chiral biphenyl diphosphine ligands and their application in asymmetric hydrogenation.

作者信息

Morimoto Toshiaki, Yoshikawa Kiyoshi, Murata Masanao, Yamamoto Naoko, Achiwa Kazuo

机构信息

School of Pharmaceutical Sciences, University of Shizuoka, Yada, Shizuoka, Japan.

出版信息

Chem Pharm Bull (Tokyo). 2004 Dec;52(12):1445-50. doi: 10.1248/cpb.52.1445.

DOI:10.1248/cpb.52.1445

PMID:15577242

Abstract

Axially chiral biphenyldiphosphine ligands bearing diphenylphosphino group(s) and/or dicyclohexylphosphino group(s) were prepared in enantiomerically pure form starting from 2,6-dimethylnitrobenzene via 8 steps: iodination, reduction, methoxylation through diazotization, Ullmann coupling, bromination, phosphorylation, optical resolution, and silane reduction, and the obtained ligands were used in rhodium-catalyzed asymmetric hydrogenation.

摘要

从2,6-二甲基硝基苯开始，通过碘化、还原、重氮化甲氧基化、乌尔曼偶联、溴化、磷酸化、光学拆分和硅烷还原等8步反应，制备了含有二苯基膦基和/或二环己基膦基的轴手性联苯二膦配体，且配体为对映体纯形式，所得配体用于铑催化的不对称氢化反应。