Preparation of Axially Chiral Biphenyl Diphosphine Ligands and Their Application in Asymmetric Hydrogenation.

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.