A readily available bisoxazolidine ligand was found to catalyze the asymmetric alkylation of aldehydes with Et(2)Zn and less reactive Me(2)Zn, providing high yields and ee's in both reactions. The bisoxazolidine-catalyzed alkylations and alkynylation of benzaldehyde show a positive nonlinear effect that cannot be accounted for by Kagan's ML(n) model. The chiral amplification originates from selective phase distribution favoring enrichment of the major enantiomer of the scalemic catalyst in solution.