Chiral Transient Directing Group Enabled Palladium-Catalyzed Atroposelective C–H Vinylation of Biaryl Aldehydes with Vinyl Silane

Herein, we report a palladium-catalyzed atroposelective C-H vinylation approach for the construction of axially chiral biaryls featuring vinyl substituents, enabled by a chiral transient directing group. Notably, this transformation proceeds efficiently with vinyl silane as the vinyl source, without requiring any external fluoride additives. This protocol exhibits a broad substrate scope, efficiently transforming diverse biaryl-2-aldehydes into atroposelective vinylated products in excellent yields with high enantioselectivities up to >99.9% ee. Additionally, mechanistic studies were performed to validate the proposed reaction pathway, and post-synthetic modifications demonstrate the synthetic utility of the methodology.