N-(Benzoyloxy)amines: an investigation of their thermal stability, synthesis, and incorporation into novel peptide constructs

✍ Scribed by Anne Nemchik; Valentina Badescu; Otto Phanstiel IV

• Book ID: 104205335
• Publisher: Elsevier Science
• Year: 2003
• Tongue: French
• Weight: 322 KB
• Volume: 59
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(03)00635-5

✦ Synopsis

A series of N-benzoyloxyamines were pyrolyzed and their decomposition temperatures correlated well with the amine architecture's ability to stabilize a N-centered radical. A variety of amine substrates were treated with a biphasic mixture of benzoyl peroxide (BPO), CH 2 Cl 2 and an aqueous carbonate buffer (at pH 10.5). Primary and secondary amines were successfully N-benzoyloxylated in good yield. Tertiary amines and BPO gave low yields of the corresponding N-oxide and complex product mixtures, presumably via radical decomposition. Electron deficient amines (such as fluorinated aliphatic amines, a-aminoacids, a-aminoesters, and a-aminoamides) were not N-benzoyloxylated under these conditions. Instead, N-benzoylation was observed with the fluorinated amines and the reaction was sensitive to temperature and the pH of the aqueous medium. A one-pot-two-step synthesis of N a -FMOC-L-Leu-N b -(benzoyloxy)-b-alanine ethyl ester, a peptide containing both an aand a novel b-amino acid framework, was also developed.