Abstract N carboxyanhydrides (NCAs) have been applied to the synthesis of peptides. Bailey has developed the application of the NCA method in peptide synthesis in which amino acids and peptide esters condense with NCAs at low temperatures in organic solvents. This reaction is known as the Bailey peptide ester synthesis. This reaction has been very useful because of rapid acylation of an amino acid and provide high yield of peptide. This method has been reported to give a free peptide from an amino acid. N‐substituted NCA has been reported as a by‐product of the reaction and can be easily removed from the conventional washing of the product with an acid or base.