Domino Aza-Annulations of Enynyl-/(Alkynyl)aryl-acetonitriles to Access Nitrogen-Enriched Heterocycles.

Unprecedented domino aza-annulations of ()-2-en-4-ynyl-acetonitriles (generated from the Morita-Baylis-Hillman acetates of propiolaldehydes for the first time) with sodium azide under metal- and oxidant-free conditions for the assembly of triazolo-pyridines are accomplished. The developed strategy offers broad substrate scope, extending to (2-alkynyl)aryl and indolyl-acetonitriles to provide the corresponding triazolo-fused isoquinolines and β-carbolines, respectively, in good yields. Additionally, the synthetic utility of the products is demonstrated via denitrogenative coupling of fused triazoles with different nucleophiles.