A synthetic method of highly substituted quinolines has been developed from <i>N</i>-(2-alkynylaryl)enamine carboxylates under Cu-catalyzed aerobic conditions via intramolecular carbo-oxygenation of alkynes. This strategy was further applied for <i>N</i>-alkynylamidines for amino-oxygenation of alkynes, leading to imidazole and quinazoline derivatives