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Formation of 1,3-Thiazol-5(4H)-imines and 1,3-Oxazol-5(4H)-imines in Aib-Containing Thiopeptides


Breitenmoser, Roland A; Linden, Anthony; Heimgartner, Heinz (2002). Formation of 1,3-Thiazol-5(4H)-imines and 1,3-Oxazol-5(4H)-imines in Aib-Containing Thiopeptides. Helvetica Chimica Acta, 85:990-1018.

Abstract

When tripeptides of type Axxt-Aib-Axx-OH were coupled with amino acid methyl esters by means of commonly used coupling reagents, the formation of 1,3-thiazol-5(4H)-imines and 1,3-oxazol-5(4H)-imines was observed. With the aim of understanding which structure elements are required for this reaction, several model peptides have been prepared according to our recently described methodology, a modification of the 'azirine/oxazolone method', followed by selective isomerization of the peptide thioamides. In addition, attempts to prepare peptides that contain more than one C=S group by the same methodology also led to the formation of 1,3-thiazol-5(4H)-imine-containing derivatives. An additional C=S group can be introduced into the peptide, when the 1,3-thiazol-5(4H)-imines were treated with H2S, although mixtures of epimers were obtained. The structures of an endothiohexapeptide, two 1,3-thiazol-5(4H)-ones, and two peptides containing a 1,3-thiazol- 5(4H)-imine moiety have been established by X-ray crystal-structure analysis.

Abstract

When tripeptides of type Axxt-Aib-Axx-OH were coupled with amino acid methyl esters by means of commonly used coupling reagents, the formation of 1,3-thiazol-5(4H)-imines and 1,3-oxazol-5(4H)-imines was observed. With the aim of understanding which structure elements are required for this reaction, several model peptides have been prepared according to our recently described methodology, a modification of the 'azirine/oxazolone method', followed by selective isomerization of the peptide thioamides. In addition, attempts to prepare peptides that contain more than one C=S group by the same methodology also led to the formation of 1,3-thiazol-5(4H)-imine-containing derivatives. An additional C=S group can be introduced into the peptide, when the 1,3-thiazol-5(4H)-imines were treated with H2S, although mixtures of epimers were obtained. The structures of an endothiohexapeptide, two 1,3-thiazol-5(4H)-ones, and two peptides containing a 1,3-thiazol- 5(4H)-imine moiety have been established by X-ray crystal-structure analysis.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2002
Deposited On:09 Oct 2013 14:26
Last Modified:02 Aug 2017 19:36
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel, Stiftung für wissenschaftliche Forschung an der Universität Zürich
Publisher DOI:https://doi.org/10.1002/1522-2675(200204)85:4<990::AID-HLCA990>3.0.CO;2-6

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