Exploring Divergent Role of Amine in Chemodivergent Synthesis of 4‐alkyl/aryl‐3H‐1,2‐Dithiole‐3‐thione and Ketothioamide

The selective synthesis of 4‐alkyl/aryl‐3H‐1,2‐dithiole‐3‐thione in THF and water‐dependent switchable product ketothioamide is demonstrated. The presented method describes explicitly the synthesis of the extremely rare positional isomer 4‐alkyl/aryl‐3H‐1,2‐dithiole‐3‐thione, a unique structure distinct from another positional isomer, 5‐alkyl/aryl‐3H‐1,2‐dithiole‐3‐thione. The unique umpolung of the nitromethyl group is exploited for solvent selective nucleophilic sulfur and amine addition. The dual role of the ‐CBr3 moiety in the substrate as a synthetic equivalent and an eliminating group is demonstrated.