Novel ring-opening coupling reactions of enantiomerically pure (3R,4S)-1-(tert-butoxycarbonyl)-3-hydroxy beta-lactams 1 with various (S)-amino acid esters 2 including proline methyl ester proceed smoothly at ambient temperature to give the corresponding dipeptides 3 bearing the norstatine residue and its analogs in excellent yields. This new coupling method is applicable to solid-phase peptide syntheses.