Reductive desymmetric silylation of biaryl bis(triflates) enabled by a chiral nickel/picolinamide complex

Abstract

Given the importance of organosilicons and atropisomerism, there is a fundamental need to develop new methods to synthesize axially chiral biaryl silanes. By use of an easily accessible chiral picolinamide as a ligand and inexpensive nickel as a catalyst, we realize a desymmetric silylation of prochiral biaryl bis(triflates) with silyl chlorides under net reductive conditions. This cross-electrophile reaction offers a new approach to preparing highly enantioenriched C₁-symmetric axially chiral platform molecules, which incorporate both a silane and a triflate moiety as two distinct docking sites for various downstream derivatizations.