Asymmetric Synthesis of Silicon‐Stereogenic Silanes by Copper‐Catalyzed Desymmetrizing Protoboration of Vinylsilanes

The catalytic asymmetric creation of silanes with silicon stereocenters is a long-sought but underdeveloped topic, and only a handful of examples have been reported. Moreover, the construction of chiral silanes containing (more than) two stereocenters is a more arduous task and remains unexploited. We herein report an unprecedented copper-catalyzed desymmetrizing protoboration of divinyl-substituted silanes with bis(pinacolato)diboron (B2 pin2 ). This method enables the facile preparation of an array of enantiomerically enriched boronate-substituted organosilanes bearing contiguous silicon and carbon stereocenters with exclusive regioselectivity and generally excellent diastereo- and enantioselectivity.