On the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations

ABSTRACT: Detailed DFT studies provide an in-depth mechanistic understanding for the use of chiral amide-based ammonium ylides in epoxidation reactions. It is shown that the used chiral auxiliary efficiently shields one face of the ylide, which thus results in an extraordinarily high stereoselectivi...

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Detalles Bibliográficos
Autores principales: Novacek, Johanna, Robiette, Raphaël, Waser, Mario
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Springer Vienna 2016
Materias:
Original Paper
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5225234/
https://www.ncbi.nlm.nih.gov/pubmed/28127093
http://dx.doi.org/10.1007/s00706-016-1866-8
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author Novacek, Johanna
Robiette, Raphaël
Waser, Mario
author_facet Novacek, Johanna
Robiette, Raphaël
Waser, Mario
author_sort Novacek, Johanna
collection PubMed
description ABSTRACT: Detailed DFT studies provide an in-depth mechanistic understanding for the use of chiral amide-based ammonium ylides in epoxidation reactions. It is shown that the used chiral auxiliary efficiently shields one face of the ylide, which thus results in an extraordinarily high stereoselectivity giving only one trans-isomer with perfect control of the absolute configuration. GRAPHICAL ABSTRACT: [Image: see text] ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00706-016-1866-8) contains supplementary material, which is available to authorized users.
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spelling pubmed-52252342017-01-24 On the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations Novacek, Johanna Robiette, Raphaël Waser, Mario Monatsh Chem Original Paper ABSTRACT: Detailed DFT studies provide an in-depth mechanistic understanding for the use of chiral amide-based ammonium ylides in epoxidation reactions. It is shown that the used chiral auxiliary efficiently shields one face of the ylide, which thus results in an extraordinarily high stereoselectivity giving only one trans-isomer with perfect control of the absolute configuration. GRAPHICAL ABSTRACT: [Image: see text] ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00706-016-1866-8) contains supplementary material, which is available to authorized users. Springer Vienna 2016-11-24 2017 /pmc/articles/PMC5225234/ /pubmed/28127093 http://dx.doi.org/10.1007/s00706-016-1866-8 Text en © The Author(s) 2016 Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
spellingShingle Original Paper
Novacek, Johanna
Robiette, Raphaël
Waser, Mario
On the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations
title On the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations
title_full On the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations
title_fullStr On the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations
title_full_unstemmed On the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations
title_short On the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations
title_sort on the origin of the stereoselectivity in chiral amide-based ammonium ylide-mediated epoxidations
topic Original Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5225234/
https://www.ncbi.nlm.nih.gov/pubmed/28127093
http://dx.doi.org/10.1007/s00706-016-1866-8
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AT wasermario ontheoriginofthestereoselectivityinchiralamidebasedammoniumylidemediatedepoxidations

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