Title

N-(Benzoyloxy)Amines: An Investigation Of Their Thermal Stability, Synthesis, And Incorporation Into Novel Peptide Constructs

Keywords

Amine oxidation; Hydroxamic acids; N-benzoyloxyamines; Thermal stability; β-peptides

Abstract

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), CH2Cl2 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, α-aminoacids, α-aminoesters, and α-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 Nα-FMOC-L-Leu-Nβ-(benzoyloxy)-β-alanine ethyl ester, a peptide containing both an α- and a novel β-amino acid framework, was also developed. © 2003 Elsevier Science Ltd. All rights reserved.

Publication Date

6-9-2003

Publication Title

Tetrahedron

Volume

59

Issue

24

Number of Pages

4315-4325

Document Type

Article

Personal Identifier

scopus

DOI Link

https://doi.org/10.1016/S0040-4020(03)00635-5

Socpus ID

0037678803 (Scopus)

Source API URL

https://api.elsevier.com/content/abstract/scopus_id/0037678803

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