We report herein an Ir-catalyzed intermolecular amino group transfer to beta-keto esters (amides) to access alpha-aminocarbonyl products with excellent chemoselectivity. The key strategy was to engineer electrophilicity of the putative Ir-nitrenoids by tuning electronic property of the kappa(2)-N,O chelating ligands, thus facilitating nucleophilic addition of enol pi-bonds of 1,3-dicarbonyl substrates.