Light‐Induced Radical C(sp²)−H Trifluorovinylation of (Hetero)arenes with a Trifluorovinyl Iodine(III) Reagent (TrFVI)

Abstract Trifluorovinyl group is an emerging and valuable motif in drug discovery and material science, especially in polymer‐related researches. However, the practical and efficient synthesis of trifluorovinylated compounds with broad structural diversity still remains a challenging task. Herein, we report the scalable synthesis of a trifluorovinyl hypervalent iodine(III) reagent, ArI(CF ═ CF 2 )OTf (TrFVI), from a bulk chemical, HFC‐134a. The first C(sp 2 )─H trifluorovinylation of (hetero)arenes is achieved using TrFVI reagent via photoredox catalysis, which shows good functional group compatibility. Furthermore, late‐stage trifluorovinylation of highly modified substrates, including drug candidates, is achieved to illustrate the powerfulness of our method. A possible radical pathway is proposed according to the mechanism study.