A stereocontrolled electrophilic amination of α-branched N-tert-butanesulfinyl ketimines was developed to construct α-aminoketone derivatives containing less accessible α-tetrasubstituted stereocenters. Stereospecific α-deprotonation of ketimines with potassium tert-butoxide gave stereodefined metalloenamine intermediates that could act as nucleophiles to attack azodicarboxylic derivatives, affording α-aminated products in high yields with excellent stereoselectivities.