The hitherto unexplored N-alkynylation of electron-withdrawing or protecting group free N-heteroarenes such as indole, carbazole and pyrrole was developed using gem-dibromoalkenes to synthesize ynamines under ligand-free copper-catalyzed domino conditions. The development methodology of ynamines was also applied in the synthesis of enynamines, multi-coupled bis-ynamines, tris-ynamines, and the natural product peyonine, demonstrating its broad synthetic scope and applications.