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A series of new (N’-substituted)-hydrazo-4-aryl1,4-dihydropyridines was successfully synthesized via a facile one-pot catalytic pathway utilizing azines and propiolate esters as starting materials and a one-dimensional copper benzotriazole-based coordination polymer as catalyst. In the absence of catalyst, the corresponding 5-substituted 4,5-dihydropyrazoles were formed in moderate to high yields. Finetuning of the catalysts allowed us to gain more insights regarding the plausible reaction mechanism.