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Issue 28, 2019
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Stereoselective deconjugation of macrocyclic α,β-unsaturated esters by sequential amidation and olefin transposition: application to enantioselective phase-transfer catalysis

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Abstract

The stereoselective synthesis of chiral macrocycles bearing two aliphatic amide functional groups is reported. After the amidation mediated by TBD, a guanidine derivative, the olefin transposition step is performed with a slight excess of t-BuOK. The products are afforded in moderate to good combined yields (up to 59%) and with an excellent syn diastereoselectivity (dr > 49 : 1). Introducing enantiopure α-branched substituents was possible and it resulted in mixtures of diastereomers, which could be tested as phase-transfer catalysts using the formation of a phenylalanine analog as a test reaction (up to 43% ee). A clear matched–mismatched situation was observed in the two diastereomeric series.

Graphical abstract: Stereoselective deconjugation of macrocyclic α,β-unsaturated esters by sequential amidation and olefin transposition: application to enantioselective phase-transfer catalysis

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Supplementary files

Article information


Submitted
14 Jun 2019
Accepted
26 Jun 2019
First published
26 Jun 2019

This article is Open Access

Org. Biomol. Chem., 2019,17, 6905-6910
Article type
Paper

Stereoselective deconjugation of macrocyclic α,β-unsaturated esters by sequential amidation and olefin transposition: application to enantioselective phase-transfer catalysis

A. Homberg, R. Hrdina, M. Vishe, L. Guénée and J. Lacour, Org. Biomol. Chem., 2019, 17, 6905
DOI: 10.1039/C9OB01355E

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