Exploring Divergent Role of Amine in Chemodivergent Synthesis of 4‐Alkyl/Aryl‐3<i>H‐</i>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 both a synthetic equivalent and an eliminating group is demonstrated.