An efficient synthetic approach towards trans-β2,3-amino acids involving anti-selective aldol, azidation and controlled hydrolysis as key steps is discussed. Apart from structural elaboration of these building blocks to homo- and hetero-dipeptides, possibility of selective endocyclic cleavage of the chiral auxiliary was advantageously used in the preparation of α,β-hybrid peptide alcohols and corresponding aldehydes, which are promising candidates for biological evaluation against proteases of therapeutic interest. © 2009 Elsevier Ltd. All rights reserved.