Fluorinated Sulfilimino Iminiums: Efficient and Versatile Sources of Perfluoroalkyl Radicals under Photoredox Catalysis

Reported herein is the use of S‐perfluoroalkyl sulfilimino iminiums as a new source of R F radicals under visible‐light photoredox catalysis (R F =CF 3 , C 4 F 9 , CF 2 Br, CFCl 2 ). These shelf‐stable perfluoroalkyl reagents, readily prepared on gram scale from the corresponding sulfoxide using a one‐pot procedure, allow the efficient photoredox‐induced oxyperfluoroalkylation of various alkenes using fac‐Ir(ppy) 3 as the photocatalyst. Importantly, spin‐trapping/electron paramagnetic resonance experiments were carried out to characterize all the radical intermediates involved in this radical/cationic process.