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Design, development and applications of copper-catalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkynes

Diaryliodonium salts have been extensively applied in organic synthesis as aryl cation equivalents. However, in the electrophilic reactions with alkenes or alkynes, only the electrophilic carbon of the diaryliodonium salts was involved while the other part of the aryl ring was not utilized. Herein,...

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Autores principales: Wang, Weilin, Zhou, Junrui, Wang, Chao, Zhang, Congdi, Zhang, Xiao-Qian, Wang, Youliang
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814649/
https://www.ncbi.nlm.nih.gov/pubmed/36697744
http://dx.doi.org/10.1038/s42004-022-00768-3
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author Wang, Weilin
Zhou, Junrui
Wang, Chao
Zhang, Congdi
Zhang, Xiao-Qian
Wang, Youliang
author_facet Wang, Weilin
Zhou, Junrui
Wang, Chao
Zhang, Congdi
Zhang, Xiao-Qian
Wang, Youliang
author_sort Wang, Weilin
collection PubMed
description Diaryliodonium salts have been extensively applied in organic synthesis as aryl cation equivalents. However, in the electrophilic reactions with alkenes or alkynes, only the electrophilic carbon of the diaryliodonium salts was involved while the other part of the aryl ring was not utilized. Herein, a reaction pattern of diaryliodonium was reported as oxa-1,4-dipoles to undergo (4 + 2) cycloaddition reactions with alkynes. Broad spectrum of the two reaction partners could be utilized in this protocol, enabling an operationally simple, high yielding, and regioselective synthetic approach to isocoumarins. Particularly, good to excellent regioselectivities were achieved for the sterically unbiased unsymmetrical diaryl acetylenes, which was challenging for other transition metal-catalyzed processes. The reaction could be scaled up with the ideal 1:1 stoichiometry and the isocoumarin type natural products Oospolactone and Thunberginol A could be obtained in one or three steps through this methodology.
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spelling pubmed-98146492023-01-10 Design, development and applications of copper-catalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkynes Wang, Weilin Zhou, Junrui Wang, Chao Zhang, Congdi Zhang, Xiao-Qian Wang, Youliang Commun Chem Article Diaryliodonium salts have been extensively applied in organic synthesis as aryl cation equivalents. However, in the electrophilic reactions with alkenes or alkynes, only the electrophilic carbon of the diaryliodonium salts was involved while the other part of the aryl ring was not utilized. Herein, a reaction pattern of diaryliodonium was reported as oxa-1,4-dipoles to undergo (4 + 2) cycloaddition reactions with alkynes. Broad spectrum of the two reaction partners could be utilized in this protocol, enabling an operationally simple, high yielding, and regioselective synthetic approach to isocoumarins. Particularly, good to excellent regioselectivities were achieved for the sterically unbiased unsymmetrical diaryl acetylenes, which was challenging for other transition metal-catalyzed processes. The reaction could be scaled up with the ideal 1:1 stoichiometry and the isocoumarin type natural products Oospolactone and Thunberginol A could be obtained in one or three steps through this methodology. Nature Publishing Group UK 2022-11-08 /pmc/articles/PMC9814649/ /pubmed/36697744 http://dx.doi.org/10.1038/s42004-022-00768-3 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as 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. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Wang, Weilin
Zhou, Junrui
Wang, Chao
Zhang, Congdi
Zhang, Xiao-Qian
Wang, Youliang
Design, development and applications of copper-catalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkynes
title Design, development and applications of copper-catalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkynes
title_full Design, development and applications of copper-catalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkynes
title_fullStr Design, development and applications of copper-catalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkynes
title_full_unstemmed Design, development and applications of copper-catalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkynes
title_short Design, development and applications of copper-catalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkynes
title_sort design, development and applications of copper-catalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkynes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814649/
https://www.ncbi.nlm.nih.gov/pubmed/36697744
http://dx.doi.org/10.1038/s42004-022-00768-3
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