Palladium-Catalyzed Enantioselective Carbene Insertion into Carbon-Silicon Bonds of Silacyclobutanes.

We report herein a highly efficient palladium-catalyzed carbene insertion into strained Si-C bonds with excellent enantioselectivity, which provides a rapid and distinct method to access silacyclopentanes with a three- or four-substituted stereocenter asymmetrically. Mechanistic studies using hybrid density functional theory suggest a catalytic cycle involving oxidative addition, carbene migratory insertion, and reductive elimination. In addition, roles of the chiral ligands in controlling the reaction enantioselectivity are also elucidated.