Photoredox-Catalyzed Transfer Thio(poly)fluoroacyloxylation of Alkenes Using Oxime-Based Surrogates

An efficient photoredox-catalyzed strategy for two-component C(sp3)–S and C(sp3)–O bond formation using bench-stable and easy-to-handle oxime-based transfer reagents is reported. The distinct fragmentation pattern of these surrogates allows for a regioselective and redox-neutral 1,2-thio(poly)fluoroacyloxylation of unactivated alkenes and styrenes by a radical-polar crossover pathway, initiated by single-electron reduction of the surrogate. This method expands the utility of oxime-based surrogates in alkene difunctionalization, offering a versatile and scalable platform for the direct, chemo-, and regioselective synthesis of thio(poly)fluoroacyloxylated products with broad functional-group compatibility under mild conditions.