We describe our results on the synthesis of fused 1,2,3‐triazolo‐1,3,6‐triazonines through a copper‐catalyzed multicomponent reaction. The products were obtained in moderate to excellent yields by the reaction of 2‐azidobenzaldehydes, substituted diaminobenzenes and a range of terminal alkynes in the presence of a catalytic amount of copper iodide, with Et3N as base, in DMSO at 100 °C. This method proved to be efficient for the combinatorial synthesis of new medium‐sized N‐heterocyclic rings with potential applications in biological studies.

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