Pd‐Catalyzed S‐to‐N Atom Swap of Benzodithiol‐3‐ones Enabled by Nitrene

Comprehensive Summary An unprecedented nitrene‐induced skeletal editing of benzodithiol‐3‐ones is demonstrated herein, which constitutes the first example of S‐to‐N atom swap of benzodithiol‐3‐ones. The Pd/C catalyst demonstrated outstanding catalytic performance in this transformation by utilizing azides as the nitrene precursors to enable efficient desulfurization and nitrogen insertion of benzodithiol‐3‐ones. The proposed reaction mechanism for this Pd‐catalyzed skeletal remodeling of benzodithiol‐3‐ones is further supported by density functional theory (DFT) calculations. The current Pd‐catalyzed S‐to‐N atom exchange reaction proceeds under mild conditions with operational simplicity, eliminating the need for inert gas protection, which endows the streamline assembly of diverse benzo[ d ]isothiazol‐3(2 H )‐ ones with excellent functional group compatibility in decent yields. Moreover, this nitrene‐induced skeletal editing strategy is amenable to late‐stage functionalization of complex azides, thereby facilitating access to benzo[ d ]isothiazol‐3(2 H )‐ones decorated with pharmacologically relevant scaffolds.