Zinc-catalyzed asymmetric alpha-amination of beta-ketocarbonyl compounds 2 using dialkyl azodicarboxylates 3 as the electrophilic nitrogen source is described. The complexes of Zn(OTF)(2) and the axially chiral phenanthroline ligands (S)-1 were identified as effective catalysts for this transformation to provide alpha-amino-beta-ketocarbonyl compounds 4 with up to 93% ee.