Electrooxidative Divergent Halocyclizations of Ambident Amides

Herein, we report a divergent electrochemical halocyclization of ambident amides that enables selective formation of either C–O or C–N bonds. Unique chemoselectivity is governed by anodic oxidation conditions, in which haliranium‐mediated C–O bond formation proceeds via chloride oxidation, while amidyl radicals guide C–N bond formation under basic conditions. Various approaches to understanding reaction mechanisms have been performed, including cyclic voltammetric analyses, experimental kinetic studies, and in silico experimentation. The developed electrooxidative synthetic method offers broad functional group tolerance, highlighting electrochemistry as a powerful tool for selective halocyclization.