Photoredox-Catalyzed Hydrofluoromethylthiolation of Unactivated Alkenes to Access Alkyl Di- and Trifluoromethyl Sulfides

Herein, a visible-light-induced photocatalytic hydrofluoromethylthiolation of unactivated alkenes for the efficient construction of aliphatic di- and trifluoromethyl sulfides (47 examples, up to 93% yield) is described. In contrast to previous methods, this protocol eliminates the need for transition metals and oxidants, employing mild and environmentally benign organic photocatalysis instead. This transformation features operational simplicity, excellent chemo- and regioselectivity, and high compatibility with unactivated alkenes while demonstrating effectiveness for late-stage functionalization of commercially available drug derivatives. Preliminary mechanistic studies suggest that a radical pathway is involved in the catalytic cycle.