Photoredox Activation of Anhydrides for the Solvent‐Controlled Switchable Synthesis of gem‐Difluoro Compounds**

Abstract The incorporation of the gem ‐difluoromethylene (CF 2 ) group into organic frameworks is highly sought due to the influence of this unit on the physicochemical and pharmacological properties of molecules. Herein we report an operationally simple, mild, and switchable protocol to access various gem ‐difluoro compounds that employs chlorodifloroacetic anhydride (CDFAA) as a low‐cost and versatile fluoroalkylating reagent. Detailed mechanistic studies revealed that electron‐transfer photocatalysis triggers mesolytic cleavage of a C−Cl bond generating a gem ‐difluoroalkyl radical. In the presence of alkene, this radical species acts as a unique intermediate that, under solvent‐controlled reaction conditions, delivers a wide range of gem ‐difluorinated γ‐lactams, γ‐lactones, and promotes oxy‐perfluoroalkylation. These protocols are flow‐ and batch‐scalable, possess excellent chemo‐ and regioselectivity, and can be used for the late‐stage diversification of complex molecules.