An unprecedented electrochemical trifluoromethylation/SO2 insertion/cyclization process has been achieved in an undivided cell in an atom‐economic fashion. The protocol relies on tandem cyclization of N‐cyanamide alkenes by using Langlois’ reagent as a source of both CF3 and SO2 under direct anodically oxidative conditions, in which two C−C bonds, two C−X bonds (N−S and S−C), and two rings were formed in a single operation. This transformation enabled efficient construction of various trifluoromethylated cyclic N‐sulfonylimines from readily accessible materials.

An unprecedented electrochemical trifluoromethylation/SO 2 insertion/cyclization process has been achieved in an undivided cell in an atom-economic fashion. The protocol relies on tandem cyclization of N-cyanamide alkenes by using Langlois reagent as a source of both CF 3 and SO 2 under direct anodically oxidative conditions, in which two C À C bonds, two C À X bonds (N À S and S À C), and two rings were formed in a single operation. This transformation enabled efficient construction of various trifluoromethylated cyclic N-sulfonylimines from readily accessible materials.

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