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A new versatile protocol for the hydroperfluoroalkylation of alkenes and alkynes using suliflimino iminiums as sources of perfluoroalkyl radicals was developed. This visible‐light‐mediated process is performed in continuous flow with high efficiency (10 min of residence time), and under mild metal‐free conditions.
We report herein a novel photoredox‐catalyzed hydrotrifluoromethylation of unsaturated systems under continuous flow. This metal‐free method is easily broadened to other perfluoroalkyl groups (RF = CF3, CFCl2, CF2Br, C4F9) thanks to the use of sulfilimino iminiums as sources of ·RF radicals. The mild reaction conditions are compatible with unactivated alkenes bearing a wide range of functionalities, as well as with alkynes for the first time.