Nickel-catalyzed decarbonylative addition of acylsilanes across alkynes via the cleavage of a carbon–silicon bond

Abstract

While hydrosilylation, the formal insertion of alkenes or alkynes into an H–Si bond, has been widely developed, analogous transformations involving inert C–Si bonds are rare due to their high bond dissociation energies. Herein, we report a nickel-catalyzed decarbonylative insertion of alkynes into the C–Si bond of acylsilanes, representing a formal insertion into an Ar–Si bond, which has not been previously achieved. Using a bulky N-heterocyclic carbene ligand (IPr*), this reaction enables the stereoselective formation of (Z)-alkenylsilanes from a range of acylsilanes and internal alkynes. This transformation not only expands the synthetic utility of acylsilanes but also illustrates a strategy for structural reprogramming through carbonyl group replacement.