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

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 SO2 from trifluoromethane sulfonyl radical generated CF3 radical and afforded the trifluoromethyl‐peroxides.