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Allylic halogenation of unsaturated amino acids

Date

2003

Authors

Easton, Christopher
Edwards, Alison
McNabb, Stephen
Merrett, Martin
O'Connell, Jenny
Simpson, Gregory Wayne
Simpson, Jamie S
Willis, Anthony

Journal Title

Journal ISSN

Volume Title

Publisher

Royal Society of Chemistry

Abstract

A range of dehydro amino acid derivatives has been prepared and subjected to halogenation using either molecular bromine or chlorine, or NBS. Allylic halogenation of the unsaturated amino acid side chains occurs through radical bromination with NBS. The procedure is complementary to treatment with chlorine, which also affords allyl halides. This latter and unusual reaction is shown through a deuterium labelling study to proceed via an ionic mechanism. The choice of NBS or chlorine for allyl halide synthesis is shown to depend on the potential to avoid competing reactions, such as halolactonization of leucine derivatives with chlorine, and hydrogen abstraction and bromine incorporation at multiple sites on treatment of isoleucine derivatives with NBS. The synthetic utility of the allyl halides prepared in this study is indicated through the synthesis of a cyclopropyl amino acid derivative and the extension of the carbon skeleton of an amino acid side chain.

Description

Keywords

Keywords: Addition reactions; Bromine compounds; Crystal structure; Derivatives; Esters; Free radicals; Halogenation; Molecular structure; Electrophilic addition; Amino acids; allyl compound; amino acid; bromine; chlorine; drug derivative; halogenated hydrocarbon;

Citation

Source

Organic and Biomolecular Chemistry

Type

Journal article

Book Title

Entity type

Access Statement

License Rights

DOI

10.1039/b303719c

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