Transition metal catalyzed carbon‐silicon bond forming reactions using chlorosilanes promoted by Grignard reagents

New catalytic CSi bond‐forming reactions using chlorosilanes are described. These reactions proceed efficiently under mild conditions by the combined use of Grignard reagents and transition metal catalysts, such as Ti, Zr, Ni, and Pd. It is proposed that ate complex intermediates formed by the reaction of transition metals with Grignard reagents play important roles as the active catalytic species. The present study demonstrates the practical use of chlorosilanes in transition metal catalyzed silylation reactions providing convenient methods for allyl‐ or vinylsilane synthesis. The reaction pathways of these transformations as well as the scope and limitations are discussed.