Computational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds

Abstract Selective oxidation is one of the most important and challenging transformations in both academic research and chemical industry. Recently, a highly selective and efficient way to synthesize biologically active γ-hydroxy-α,β-unsaturated molecules from Cu-catalyzed vinylogous aerobic oxidati...

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Autores principales:	Ting Wang, Yu Zhou, Yao Xu, Gui-Juan Cheng
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2021
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/773a688c7a5140b8a8ed307fc898bedd
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spelling	oai:doaj.org-article:773a688c7a5140b8a8ed307fc898bedd2021-12-02T14:01:34ZComputational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds10.1038/s41598-020-80188-22045-2322https://doaj.org/article/773a688c7a5140b8a8ed307fc898bedd2021-01-01T00:00:00Zhttps://doi.org/10.1038/s41598-020-80188-2https://doaj.org/toc/2045-2322Abstract Selective oxidation is one of the most important and challenging transformations in both academic research and chemical industry. Recently, a highly selective and efficient way to synthesize biologically active γ-hydroxy-α,β-unsaturated molecules from Cu-catalyzed vinylogous aerobic oxidation of α,β- and β,γ-unsaturated compounds has been developed. However, the detailed reaction mechanism remains elusive. Herein, we report a density functional theory study on this Cu-catalyzed vinylogous aerobic oxidation of γ,γ-disubstituted α,β- and β,γ-unsaturated isomers. Our computational study unveils detailed mechanism for each elementary step, i.e. deprotonation, O2 activation, and reduction. Besides, the origin of regioselectivity, divergent reactivities of substrates as well as reducing agents, and the byproduct generation have also been investigated. Notably, the copper catalyst retains the + 2 oxidation state through the whole catalytic cycle and plays essential roles in multiple steps. These findings would provide hints on mechanistic studies and future development of transition metal-catalyzed aerobic oxidation reactions.Ting WangYu ZhouYao XuGui-Juan ChengNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 11, Iss 1, Pp 1-12 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Ting Wang Yu Zhou Yao Xu Gui-Juan Cheng Computational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds
description	Abstract Selective oxidation is one of the most important and challenging transformations in both academic research and chemical industry. Recently, a highly selective and efficient way to synthesize biologically active γ-hydroxy-α,β-unsaturated molecules from Cu-catalyzed vinylogous aerobic oxidation of α,β- and β,γ-unsaturated compounds has been developed. However, the detailed reaction mechanism remains elusive. Herein, we report a density functional theory study on this Cu-catalyzed vinylogous aerobic oxidation of γ,γ-disubstituted α,β- and β,γ-unsaturated isomers. Our computational study unveils detailed mechanism for each elementary step, i.e. deprotonation, O2 activation, and reduction. Besides, the origin of regioselectivity, divergent reactivities of substrates as well as reducing agents, and the byproduct generation have also been investigated. Notably, the copper catalyst retains the + 2 oxidation state through the whole catalytic cycle and plays essential roles in multiple steps. These findings would provide hints on mechanistic studies and future development of transition metal-catalyzed aerobic oxidation reactions.
format	article
author	Ting Wang Yu Zhou Yao Xu Gui-Juan Cheng
author_facet	Ting Wang Yu Zhou Yao Xu Gui-Juan Cheng
author_sort	Ting Wang
title	Computational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds
title_short	Computational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds
title_full	Computational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds
title_fullStr	Computational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds
title_full_unstemmed	Computational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds
title_sort	computational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds
publisher	Nature Portfolio
publishDate	2021
url	https://doaj.org/article/773a688c7a5140b8a8ed307fc898bedd
work_keys_str_mv	AT tingwang computationalexplorationofcoppercatalyzedvinylogousaerobicoxidationofunsaturatedcompounds AT yuzhou computationalexplorationofcoppercatalyzedvinylogousaerobicoxidationofunsaturatedcompounds AT yaoxu computationalexplorationofcoppercatalyzedvinylogousaerobicoxidationofunsaturatedcompounds AT guijuancheng computationalexplorationofcoppercatalyzedvinylogousaerobicoxidationofunsaturatedcompounds
_version_	1718392148367245312

Computational exploration of copper catalyzed vinylogous aerobic oxidation of unsaturated compounds

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