Synthesis of 5‐Trifluoromethylpyrroles from Heating‐Induced Annulation of Pyridinium 1,4‐Zwitterionic Thiolates with CF3‐Imidoyl Sulfoxonium Ylides

Abstract A heating‐induced desulfuration annulation of pyridinium 1,4‐zwitterionic thiolates and CF 3 ‐substituted imidoyl sulfoxonium ylides has been achieved, allowing a route to biologically important 5‐trifluoromethylpyrroles. The transformation proceeds through an unusual ((3+3)‐1) pathway under metal‐free conditions with the extrusion of 4‐methoxypyridine, sulfur and DMSO. The scale‐up reaction and further transformation of the obtained pyrrole products have been performed to demonstrate the synthetic utility of the developed method.