Affiliation:
1. CAS Key Laboratory of Synthetic Chemistry of Natural Substances Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
Abstract
AbstractHerein, a copper(I)‐catalyzed asymmetric hydrophosphination of 3,3‐disubstituted cyclopropenes is reported. It provides a series of phosphine derivatives in high to excellent diastereo‐ and enantioselectivities. The methodology enjoys broad substrate scope on both 3,3‐disubstituted cyclopropenes and diarylphosphines. The high stereoselectivity is attributed to both the high stability of the Cu(I)‐(R,R)‐QUINOXP* complex in the presence of stoichiometric HPPh2 and the produced phosphines, and the high‐performance asymmetric induction of the Cu(I)‐(R,R)‐QUINOXP* complex. Finally, the method is used for the synthesis of new chiral phosphine‐olefin compounds built on a cyclopropane skeleton, one of which serves as a wonderful ligand in Rh‐catalyzed asymmetric conjugate addition of phenylboronic acid to various α,β‐unsaturated compounds.