An approach for the construction of 5trifluoromethyl-1,4-dihydro-1,2,4-triazines has been developed via base-mediated [3 + 3] cycloaddition of in-situ generated nitrile imines and CF 3 -substituted imidoyl sulfoxonium ylides. The metal-free protocol is characterized by readily available starting materials, mild conditions, a broad substrate scope, high efficiency, good synthetic prospect, and scalability.

An efficient and straightforward approach for the synthesis of trifluoromethyl-decorated benzo[de][1,8]naphthyridines has been achieved via the Rh(III)-catalyzed dual C–H activation and cascade annulation of benzimidates and CF3-imidoyl sulfoxonium ylides. The novel transformation involves the formation of four new chemical bonds along with the release of two molecules of dimethyl sulfoxide (DMSO) and one molecule each of ethanol and amine. The optoelectronic properties of the obtained fused aromatic products have been investigated by recording the UV–vis absorption and emission spectra.

A heating‐induced desulfuration annulation of pyridinium 1,4‐zwitterionic thiolates and CF3‐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.