Herein, we report that a metal-free multicomponent strategy integrates Kornblum oxidation, dehydrative condensation, Willgerodt–Kindler-type polysulfuration, and heterocyclization, enabling the synthesis of bioactive 1,2,3-dithiazole-5-thione scaffolds from readily accessible methyl ketones, elemental sulfur, and cyanamides. In this protocol, S 8 serves as the triple sulfur donor for both the CS and S 2 moieties, while cyanamides provide the nitrogen source. Remarkably, this method accomplishes the cleavage of triple Csp 3 H bonds and...