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

    Authors

    A. Nemchik; V. Badescu;O. Phanstiel

    Comments

    Authors: contact us about adding a copy of your work at STARS@ucf.edu

    Abbreviated Journal Title

    Tetrahedron

    Keywords

    thermal stability; amine oxidation; N-benzoyloxyamines; hydroxamic; acids; beta-peptides; AMINES; CHEMISTRY; ACIDS; Chemistry, Organic

    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, alpha-aminoacids, alpha-aminoesters, and alpha-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-alpha-FMOC-L-Leu-N-beta-(benzoyloxy)-beta-alanine ethyl ester, a peptide containing both an alpha- and a novel beta-amino acid framework, was also developed. (C) 2003 Elsevier Science Ltd. All rights reserved.

    Journal Title

    Tetrahedron

    Volume

    59

    Issue/Number

    24

    Publication Date

    1-1-2003

    Document Type

    Article

    Language

    English

    First Page

    4315

    Last Page

    4325

    WOS Identifier

    WOS:000183358200010

    ISSN

    0040-4020

    Share

    COinS