Remarkably diastereoselective synthesis of a chiral biphenyl diphosphine ligand and its application in asymmetric hydrogenation.
Essentially complete atropdiastereoselectivity was realized in the preparation of biaryl diphosphine dioxide by asymmetric intramolecular Ullmann coupling and oxidative coupling with central-to-axial chirality transfer. A bridged C(2)-symmetric biphenyl phosphine ligand possessing additional chiral centers on the linking unit of the biphenyl groups was synthesized. No resolution step was required for the preparation of the enantiomerically pure chiral ligand. These findings offer a general and practical tool for the development of previously uninvestigated atropdiastereomeric biaryl phosphine ligands. The diphosphine ligand was found to be highly effective in the asymmetric hydrogenation of alpha- and beta-ketoesters, 2-(6'-methoxy-2'-naphthyl)propenoic acid, beta-(acylamino)acrylates, and enol acetates.
Qiu
Liqin
L
Open Laboratory of Chirotechnology of the Institute of Molecular Technology for Drug Discovery and Synthesis and Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong.
Wu
Jing
J
Chan
Shusun
S
Au-Yeung
Terry T-L
TT
Ji
Jian-Xin
JX
Guo
Rongwei
R
Pai
Cheng-Chao
CC
Zhou
Zhongyuan
Z
Li
Xingshu
X
Fan
Qing-Hua
QH
Chan
Albert S C
AS