Rhodium(I)-[2-[2-(dimethylamino)ethyl]-1,3-propanediyl]bis(diphenylphosphine) (DPP-AE) catalyst achieved an effective 1,4-asymmetric induction and afforded high diastereoselectivity (max. 96% d.e.) in the hydrogenation of dehydrodipeptides in protic solvents. Activation parameters indicate the important role of the electrostatic interaction for the asymmetric induction in the hydrogenation. Structural study of the rhodium(I) DPP-AE complex by 31P NMR and circular dichroism spectroscopies indicated that induced fitting of the complex occurred by the electrostatic interaction between the ligand (DPP-AE) and dehydrodipeptide to change the dominant skew-conformation of the complex according to the chiral center of the substrate. © 1997 Elsevier Science S.A.