Enantioselective carboaminations of olefins constitute an attractive strategy for a rapid increase in molecular complexity from readily available starting materials. Reported here is an intermolecular asymmetric carboamination of acrylates using rhodium(III)-catalyzed alkenyl C-H activations of N-enoxysuccinimides to generate the nitrogen and carbon portion for the transfer. A rhodium complex equipped with a tailored bulky trisubstituted chiral Cp-x ligand ensures carboamination chemoselectivity as well high levels of enantioinduction. The transformation operates under mild reaction conditions at ambient temperatures and provides access to a variety of alpha-amino esters in good yields and excellent enantiomeric ratios of >99.5:0.5.