Direct α-C–H Alkylation of Alcohols with Alkenes

Herein, we report a direct α-C-H alkylation of alcohols with alkenes enabled by organic photoredox catalysis, in which the additive trimethylsilyl azide (TMSN₃) plays a crucial role in the selective activation of the α-C-H bond of free alcohols. Both α-CF₃-alkenes and acrylamides showed high efficiency and excellent chemoselectivity in this transformation, affording various γ-trifluoromethyl alcohols and γ-hydroxyl amides under mild conditions. The late-stage modification of several drug derivatives was achieved, and the synthetic utility of this protocol was further highlighted by the scaled-up reaction and several derivations of the products.