Bis(trifluoromethyl)thione S-imides are synthesised via 1,3-dehydrochlorination 1. ▪ These compounds are versatile precursors for the preparation of heterocycles. They undergo [3+2] cycloaddition reactions to afford five-membered, bis(trifluoromethyl)substituted heterocycles in high yields. The heterocyclic compounds are fully characterised by n.m.r, and elemental analyses, and single crystal X-ray structures of selected examples will be presented. Furthermore, the use of 1 as a ligand in the synthesis of metal complexes will be discussed.