Issue 8, 2015

Remote stereoselective deconjugation of α,β-unsaturated esters by simple amidation reactions

Abstract

The thermodynamically disfavored isomerization of α,β-unsaturated esters to deconjugated β,γ-unsaturated analogues occurs readily when coupled to an amidation. Within the framework of macrocyclic derivatives, it is shown that 15, 16, and 18 membered macrocycles react with tBuOK and anilines to generate, in one-pot, β,γ-unsaturated amides (yields up to 88%). Importantly, single (chiral) diastereomers are isolated (d.r. > 49 : 1, 1H NMR) irrespective of the size and nature of the rings, showing an effective transmission of remote stereochemistry during the isomerization process. CSP-chromatographic resolution and absolute configuration determination by VCD are achieved.

Graphical abstract: Remote stereoselective deconjugation of α,β-unsaturated esters by simple amidation reactions

Supplementary files

Article information

Article type
Edge Article
Submitted
27 Mar 2015
Accepted
21 May 2015
First published
25 May 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2015,6, 4923-4928

Remote stereoselective deconjugation of α,β-unsaturated esters by simple amidation reactions

M. Vishe, R. Hrdina, A. I. Poblador-Bahamonde, C. Besnard, L. Guénée, T. Bürgi and J. Lacour, Chem. Sci., 2015, 6, 4923 DOI: 10.1039/C5SC01118C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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