Enantioselective Construction of Si-Stereogenic Linear Alkenylhy-drosilanes via Copper-Catalyzed Anti-Markovnikov Hydrosilyla-tion of Alkynes

Abstract

Herein we report an unprecedented copper-catalyzed asymmetric anti-Markovnikov hydrosilylation of alkynes with dihydrosilanes for the synthesis of silicon-stereogenic alkenyl silanes in good regio- and enantioselectivities. Demonstrated by a diverse collection of substrates, the process grants access to chiral alkenylhydrosilanes with a simple Cu/(S)-Tol-BINAP catalytic system. The origin of the enantiocontrol was investigated by density functional theory (DFT) calculations, which revealed a quite complicated scenario involving multiple pairs of diastereomeric transition structures accounting for the high enantiocontrol under the seemingly simple conditions.