Acyclic α-amino nitriles 1, derived from α-alkylbenzylamines 3 and aldehydes 4 via a Strecker-type reaction, readily epimerize in MeOH at the newly emerged asymmetric center α to the cyano group. The equilibrium diastereomeric ratio [(R * , R * )-1]:[(R * ,S * )-1] varies from 73:27 for 1e to 90:10 for 1h. The latter ratio is unprecedentedly high for thermodynamically controlled 1,3-asymmetric induction. The aromatic group and a bulky alkyl group (R 1 ) of the parent amine 3 are required to obtain high concentrations of (R * , R * )-1, whereas the bulkiness of the alkyl group (R 2 ) of the parent aldehyde 4 has little effect. The reasons for the thermodynamic predominance of (R * ,R * )-1 over (R * ,S * )-1 were addressed by MM2 calculations, which predicted the most stable conformers of (R * ,R * )-1 and (R * ,S * )-1. The structures of these conformers were verified by 1 H NMR spectroscopy and X-ray crystallography