Catalytic enantioselective alkylations of three classes of ketoimines are reported. Reactions are promoted in the presence 0.5–10 mol % of a Zr salt and a chiral ligand that contains two inexpensive amino acids (valine and phenylalanine) and involve Me₂Zn or Et₂Zn as alkylating agents. Requisite aryl- and alkyl-substituted α-ketoimine esters, accessed readily and in >80% yield on gram scale through a two-step sequence from the corresponding ketones, undergo alkylation to afford quaternary α-amino esters in 79–97% ee. Aryl-substituted trifluoroketoimines are converted to the corresponding amines by reactions with Me₂Zn, catalyzed by a chiral complex that bears a modified N-terminus. The utility of the catalytic asymmetric protocols is illustrated through conversion of the enantiomerically enriched alkylation products to a range of cyclic and acyclic compounds bearing an N-substituted quaternary carbon stereogenic center.