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Scope and Limitation of the Acid-Catalyzed Isomerization of Aib-Containing Thiopeptides


Breitenmoser, Roland A; Heimgartner, Heinz (2001). Scope and Limitation of the Acid-Catalyzed Isomerization of Aib-Containing Thiopeptides. Helvetica Chimica Acta, 84(4):786-796.

Abstract

The use of amino thio S-acids in the 'azirine/oxazolone method' and a novel isomerization led to Aib-containing endothiopeptides. With the aim of generalizing this method, a variety of Aib-containing dipeptide thioanilides have been prepared. By their treatment with ZnCl2 in AcOH, followed by HCl-saturated AcOH, the C=S group was shifted from the last to the penultimate amino acid in high yield and without epimerization. As this methodology is very useful for the specific introduction of a thioamide group, it was extended to Aib-containing tripeptides. In addition, it could be shown that a mechanism via spirocyclic intermediates (cf. Scheme 4) is most likely for this isomerization. To establish the proposed neighboring-group participation of the N-acyl group, model dipeptide thioanilides containing no N-terminal C=O group were synthesized. These derivatives did not undergo rearrangement.

Abstract

The use of amino thio S-acids in the 'azirine/oxazolone method' and a novel isomerization led to Aib-containing endothiopeptides. With the aim of generalizing this method, a variety of Aib-containing dipeptide thioanilides have been prepared. By their treatment with ZnCl2 in AcOH, followed by HCl-saturated AcOH, the C=S group was shifted from the last to the penultimate amino acid in high yield and without epimerization. As this methodology is very useful for the specific introduction of a thioamide group, it was extended to Aib-containing tripeptides. In addition, it could be shown that a mechanism via spirocyclic intermediates (cf. Scheme 4) is most likely for this isomerization. To establish the proposed neighboring-group participation of the N-acyl group, model dipeptide thioanilides containing no N-terminal C=O group were synthesized. These derivatives did not undergo rearrangement.

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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:2001
Deposited On:23 Oct 2013 06:40
Last Modified:05 Apr 2016 17:03
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(20010418)84:4<786::AID-HLCA786>3.0.CO;2-A

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