An operationally simple domino approach for the silver-catalyzed synthesis of oxazine/benzoxazine-fused isoquinolines 5a鈥?b>q and naphthyridines 6a鈥?b>v by the reaction of o-alkynyl aldehydes 3a鈥?b>aa with amines having embedded nucleophiles 4a鈥?b>d under mild reaction condition in water is described. The reaction shows selective C鈥揘 bond formation on the more electrophilic alkynyl carbon resulting in the formation of 6-endo-dig cyclized product. The competitive experiments show the viability of an intramolecular nucleophilic attack over an intermolecular attack of the external nucleophile. This methodology accommodates wide functional group variation, which proves to be useful for structural and biological assessment.