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Atom-economic generation of gold carbenes: gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles

The generation of gold carbenes via the gold-catalyzed intermolecular reaction of nucleophiles containing relatively labile N–O or N–N bonds with alkynes has received considerable attention during recent years. However, this protocol is not atom-economic as the reaction produces a stoichiometric amo...

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Autores principales: Zhou, Ai-Hua, He, Qiao, Shu, Chao, Yu, Yong-Fei, Liu, Shuang, Zhao, Tian, Zhang, Wei, Lu, Xin, Ye, Long-Wu
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5811108/
https://www.ncbi.nlm.nih.gov/pubmed/29560212
http://dx.doi.org/10.1039/c4sc02596b
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author Zhou, Ai-Hua
He, Qiao
Shu, Chao
Yu, Yong-Fei
Liu, Shuang
Zhao, Tian
Zhang, Wei
Lu, Xin
Ye, Long-Wu
author_facet Zhou, Ai-Hua
He, Qiao
Shu, Chao
Yu, Yong-Fei
Liu, Shuang
Zhao, Tian
Zhang, Wei
Lu, Xin
Ye, Long-Wu
author_sort Zhou, Ai-Hua
collection PubMed
description The generation of gold carbenes via the gold-catalyzed intermolecular reaction of nucleophiles containing relatively labile N–O or N–N bonds with alkynes has received considerable attention during recent years. However, this protocol is not atom-economic as the reaction produces a stoichiometric amount of pyridine or quinoline waste, the cleaved part of the N–O or N–N bonds. In this article, we disclose an unprecedented gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles, allowing rapid and practical access to a wide range of synthetically-useful 2-aminopyrroles. Most importantly, mechanistic studies and theoretical calculations revealed that this reaction presumably proceeds via an α-imino gold carbene pathway, thus providing a strategically novel, atom-economic route to the generation of gold carbenes. Other significant features of this approach include the use of readily-available starting materials, high flexibility, simple procedure, mild reaction conditions, and in particular, no need to exclude moisture or air (“open flask”).
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spelling pubmed-58111082018-03-20 Atom-economic generation of gold carbenes: gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles Zhou, Ai-Hua He, Qiao Shu, Chao Yu, Yong-Fei Liu, Shuang Zhao, Tian Zhang, Wei Lu, Xin Ye, Long-Wu Chem Sci Chemistry The generation of gold carbenes via the gold-catalyzed intermolecular reaction of nucleophiles containing relatively labile N–O or N–N bonds with alkynes has received considerable attention during recent years. However, this protocol is not atom-economic as the reaction produces a stoichiometric amount of pyridine or quinoline waste, the cleaved part of the N–O or N–N bonds. In this article, we disclose an unprecedented gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles, allowing rapid and practical access to a wide range of synthetically-useful 2-aminopyrroles. Most importantly, mechanistic studies and theoretical calculations revealed that this reaction presumably proceeds via an α-imino gold carbene pathway, thus providing a strategically novel, atom-economic route to the generation of gold carbenes. Other significant features of this approach include the use of readily-available starting materials, high flexibility, simple procedure, mild reaction conditions, and in particular, no need to exclude moisture or air (“open flask”). Royal Society of Chemistry 2015-02-01 2014-11-12 /pmc/articles/PMC5811108/ /pubmed/29560212 http://dx.doi.org/10.1039/c4sc02596b Text en This journal is © The Royal Society of Chemistry 2014 http://creativecommons.org/licenses/by/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Zhou, Ai-Hua
He, Qiao
Shu, Chao
Yu, Yong-Fei
Liu, Shuang
Zhao, Tian
Zhang, Wei
Lu, Xin
Ye, Long-Wu
Atom-economic generation of gold carbenes: gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles
title Atom-economic generation of gold carbenes: gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles
title_full Atom-economic generation of gold carbenes: gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles
title_fullStr Atom-economic generation of gold carbenes: gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles
title_full_unstemmed Atom-economic generation of gold carbenes: gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles
title_short Atom-economic generation of gold carbenes: gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles
title_sort atom-economic generation of gold carbenes: gold-catalyzed formal [3+2] cycloaddition between ynamides and isoxazoles
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5811108/
https://www.ncbi.nlm.nih.gov/pubmed/29560212
http://dx.doi.org/10.1039/c4sc02596b
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