CuBr2-catalyzed three-component coupling of N-benzylallylamine, ethyl glyoxalate, and terminal alkynes afforded glycine-tethered 1,6-enynes, which were further transformed into polycyclic pyrrole-2-carboxylates via novel cycloisomerization/Diels-Alder cycloaddition/dehydrogenation sequence under iridium-catalyzed conditions.