Abstract

AbstractA photoredox‐catalyzed trifluoromethylthiolation process of aromatic alkenes has been developed. A strongly reducing photocatalyst, fac‐[Ir(4‐MeO‐ppy)3] (4‐MeO‐ppy=2‐pyridyl‐5‐methoxyphenyl), and an electrophilic trifluoromethylthiolating reagent, 1‐(trifluoromethylthio)pyrrolidine‐2,5‐dione (1 a), play key roles in the efficient generation of a trifluoromethansulfenyl radical (.SCF3). The well‐designed photoredox system induces a single‐step, regioselective installation of a CF3S and a hydroxy or an alkoxy group onto vicinal carbon atoms through redox‐neutral processes. The present oxytrifluoromethylthiolation features mild reaction conditions without extra additives for the activation of the CF3S reagent, making the present protocol applicable to a wide variety of functionalized aromatic alkenes.

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