Merging Copper(I) Photoredox Catalysis and Iodine(III) Chemistry for the Oxy‐monofluoromethylation of Alkenes

A simple process for the oxy-monofluoromethylation of alkenes is described. In combination with visible-light copper(I) photoredox catalysis, an easily accessible iodine(III) reagent containing monofluoroacetoxy ligands serves as a powerful source of a monofluoromethyl (CH2 F) radical, enabling the step economical synthesis of γ-fluoro-acetates from a broad range of olefinic substrates under mild conditions. Applications to late-stage diversification of alkenes derived from complex molecules, amino acids and the synthesis of fluoromethylated heterocycles are also demonstrated.