alkylation of sulfinicacids with sulfonamides has been developed via sp3 C−N bond cleavage at room temperature. In the absence of external catalysts and additives, a wide variety of N-benzylic and N-allylic sulfonamides couple with sulfinicacids to give structurally diversified sulfones in moderate to excellent yields. Furthermore, the reaction of N-(2-acyl)allylic sulfonamides with sulfinicacids provides