Photocatalytic Vicinal Trifluoromethylation and Disulfuration of Alkenes Using Langlois' Reagent and Tetrasulfides

Comprehensive Summary In this study, we outline a versatile method for the preparation of trifluoromethyl‐containing unsymmetrical disulfides via catalytic photoredox difunctionalization of alkenes using symmetrical tetrasulfide (RSSSSR) and Langlois' reagent (CF₃SO₂Na). Notably, this method is also suitable for the late‐stage modification of pharmaceutical molecule derivatives. Furthermore, a set of experimental investigations, such as radical trapping experiment, scrambling experiment, cyclic voltammetry (CV) measurement, Stern‐Volmer analysis, on/off light‐control experiments and a radical cascade experiment have been performed to support the photocatalytic reductive quenching cycle and radical‐radical coupling reaction pathway.