Conclusive Evidence for an S_N2‐Si Mechanism in the B(C₆F₅)₃‐Catalyzed Hydrosilylation of Carbonyl Compounds: Implications for the Related Hydrogenation

Abstract

Just ask silicon: An experimentally straightforward yet effective Walden-type analysis showcases the usefulness of silanes with a stereogenic silicon center as stereochemical probes. The B(C6F5)3-catalyzed hydrosilylation and likely the related hydrogenation proceed through linear B-H-Si-O transition states, as verified by flawless inversion of the absolute configuration at silicon (see scheme).