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Aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide
The organocatalytic epoxidation of unactivated alkenes using aqueous hydrogen peroxide provides various indispensable products and intermediates in a sustainable manner. While formyl functionalities typically undergo irreversible oxidations when activating an oxidant, an atropisomeric two-axis aldeh...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8336450/ https://www.ncbi.nlm.nih.gov/pubmed/34377408 http://dx.doi.org/10.1039/d1sc02360h |
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author | Triandafillidi, Ierasia Kokotou, Maroula G. Lotter, Dominik Sparr, Christof Kokotos, Christoforos G. |
author_facet | Triandafillidi, Ierasia Kokotou, Maroula G. Lotter, Dominik Sparr, Christof Kokotos, Christoforos G. |
author_sort | Triandafillidi, Ierasia |
collection | PubMed |
description | The organocatalytic epoxidation of unactivated alkenes using aqueous hydrogen peroxide provides various indispensable products and intermediates in a sustainable manner. While formyl functionalities typically undergo irreversible oxidations when activating an oxidant, an atropisomeric two-axis aldehyde capable of catalytic turnover was identified for high-yielding epoxidations of cyclic and acyclic alkenes. The relative configuration of the stereogenic axes of the catalyst and the resulting proximity of the aldehyde and backbone residues resulted in high catalytic efficiencies. Mechanistic studies support a non-radical alkene oxidation by an aldehyde-derived dioxirane intermediate generated from hydrogen peroxide through the Payne and Criegee intermediates. |
format | Online Article Text |
id | pubmed-8336450 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-83364502021-08-09 Aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide Triandafillidi, Ierasia Kokotou, Maroula G. Lotter, Dominik Sparr, Christof Kokotos, Christoforos G. Chem Sci Chemistry The organocatalytic epoxidation of unactivated alkenes using aqueous hydrogen peroxide provides various indispensable products and intermediates in a sustainable manner. While formyl functionalities typically undergo irreversible oxidations when activating an oxidant, an atropisomeric two-axis aldehyde capable of catalytic turnover was identified for high-yielding epoxidations of cyclic and acyclic alkenes. The relative configuration of the stereogenic axes of the catalyst and the resulting proximity of the aldehyde and backbone residues resulted in high catalytic efficiencies. Mechanistic studies support a non-radical alkene oxidation by an aldehyde-derived dioxirane intermediate generated from hydrogen peroxide through the Payne and Criegee intermediates. The Royal Society of Chemistry 2021-06-21 /pmc/articles/PMC8336450/ /pubmed/34377408 http://dx.doi.org/10.1039/d1sc02360h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Triandafillidi, Ierasia Kokotou, Maroula G. Lotter, Dominik Sparr, Christof Kokotos, Christoforos G. Aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide |
title | Aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide |
title_full | Aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide |
title_fullStr | Aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide |
title_full_unstemmed | Aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide |
title_short | Aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide |
title_sort | aldehyde-catalyzed epoxidation of unactivated alkenes with aqueous hydrogen peroxide |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8336450/ https://www.ncbi.nlm.nih.gov/pubmed/34377408 http://dx.doi.org/10.1039/d1sc02360h |
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