Radical Haloazidation of 1,5-Enenitriles for Making N -Haloimines and Sequential Triazolation to Form Tricyclics

A new method for making N-haloimines by Mn-catalyzed radical haloazidation of 1,5-enenitriles with TMSN₃ and N-halosuccinimides is introduced. The resulting azido N-haloimines are used for diannulation with alkynes to form triazole-fused heterocycles via a cascade CuAAC with alkynes and intramolecular electrophilic aromatic substitution (EAS).