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.