Abstract: Enantioenriched unnatural amino acids represent a prevalent motif in organic chemistry, with profound applicationsin biochemistry, medicinal chemistry, and materials science. Herein, we report a cobalt-catalyzed aza-Barbier reaction ofdehydroglycines with unactivated alkyl halides to afford unnatural α-amino esters with high enantioselectivity. This catalyticreductive alkylative addition protocol circumvents the use of moisture-, air-sensitive organometallic reagents, and stoichiometricchiral auxiliaries, enabling the conversion of a variety of primary, secondary, and even tertiary unactivated alkyl halides to α-alkyl-amino esters under mild conditions, thus leading to broad functional group tolerance. The expedient access to biologically activemotifs demonstrates the practicality of this protocol by reducing the number of synthetic steps and enhancing the reaction efficiency.