Asymmetric Catalytic Reactions Using <i>P*</i>‐Mono‐, <i>P*,N</i>‐ and <i>P*,P*</i>‐Bidentate Diamidophosphites with BINOL Backbones and 1,3,2‐Diazaphospholidine Moieties: Differences in the Enantioselectivity

Abstract

Abstract A new series of P *‐chiral diamidophosphites with 1,3,2‐diazaphospholidine rings, based on ( S a )‐ or ( R a )‐BINOL and their easily accessible derivatives, has been synthesized for the first time and tested in asymmetric transition metal catalysis. Up to 99% ee was achieved in the rhodium‐catalyzed asymmetric hydrogenation of functionalized olefins and in the palladium‐catalyzed allylic substitution. The influence of the nature of the donor atoms and denticity on the asymmetric induction is discussed. In addition, the first example of a successful platinum‐catalyzed asymmetric allylic amination (up to 86% ee ) with participation of organophosphorus ligands is considered.