N‐Formylation of Amino Acid Esters and Peptides via Peroxide–Mediated Decarboxylative Coupling with α‐Keto Acids

N ‐formyl amino acids and peptides play a crucial role in protein biosynthesis and in the design and development of antimicrobial peptides. In this study, we report an efficient N ‐formylation of amino acid esters and peptides with α‐keto acids via peroxide‐mediated decarboxylative coupling, where only water/tertiary butanol and carbon dioxide were formed as by‐products. H 2 O 2 was found to be ideal for the N ‐formylation of substituted amino acids, while TBHP was successful for unprotected amino acid esters and oligopeptides. The methodology was extended for the synthesis of bioactive N ‐formyl methionine and f‐MLP. The synthesized library includes N ‐ferrocenyl‐ N ‐formyl amino acid and peptide derivatives, which might serve as a hybrid material for medicinal and electrochemical applications.