Photo‐Induced Sulfonylation/Trifluoromethylation‐Peroxidation of Alkenes via EnT‐Mediated N−S Bond Homolysis of N‐Sulfonyl Ketimines

Abstract Photocatalytic sulfonylation/trifluoromethylation‐peroxidation of alkenes with N ‐sulfonyl ketimines and tert ‐butyl hydroperoxide is reported. The transformation is initiated by the EnT‐driven homolytic S− N bond cleavage of N ‐sulfonyl ketimines. The sulfonyl‐peroxides were obtained when alkyl sulfonyl radicals were captured by alkene via sequential C−S and C−O bond formation, while a thermodynamically favored release of SO 2 from trifluoromethane sulfonyl radical generated CF 3 radical and afforded the trifluoromethyl‐peroxides.