Controllable Regioselective [3+2] Cyclizations of N-CF₃ Imidoyl Chlorides and Ph₃PNNC: Divergent Synthesis of N-CF₃ Triazoles

Presented herein are two distinct regiodivergent [3+2] cyclization reactions between N-CF3 imidoyl chlorides and N-isocyaniminotriphenylphosphorane (NIITP) that include flexible modulation of the electronic properties of NIITP. The regioselectivity of reactions was different in the absence and presence of the Mo catalyst. The approach provides alternative efficient and scalable routes for N-CF3 triazole synthesis, demonstrating a broad substrate scope, excellent functional group tolerance, and practical advantages.