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

Abstract

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(2H)- 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(2H)-ones decorated with pharmacologically relevant scaffolds.