Abstract3‐Substituted‐5‐phenylmorpholinones have been demonstrated to act asN‐protectedC‐terminus activated α‐amino acids capable of undergoing solution phaseN‐terminus peptide extension following standard coupling procedures. TheN‐acylated morpholinones do not undergo epimerisation of the stereocentre of theC‐terminus amino acid residue as oxazolone formation is sterically prevented, althoughC‐terminus peptide coupling is still possible. This convergent approach to peptide synthesis is exemplified by the preparation of L‐ala‐L‐ala‐L‐ala and L‐ala‐D‐ala‐L‐ala. Copyright © 2008 European