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Divergent rhodium-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes
α-Pyridones and α-pyrones are ubiquitous structural motifs found in natural products and biologically active small molecules. Here, we report an Rh-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes, affording cyclic products in good to excellent yield. Divergent syntheses...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7876044/ https://www.ncbi.nlm.nih.gov/pubmed/33568643 http://dx.doi.org/10.1038/s41467-021-21190-8 |
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author | Xing, Yi-Kang Chen, Xin-Ran Yang, Qi-Liang Zhang, Shuo-Qing Guo, Hai-Ming Hong, Xin Mei, Tian-Sheng |
author_facet | Xing, Yi-Kang Chen, Xin-Ran Yang, Qi-Liang Zhang, Shuo-Qing Guo, Hai-Ming Hong, Xin Mei, Tian-Sheng |
author_sort | Xing, Yi-Kang |
collection | PubMed |
description | α-Pyridones and α-pyrones are ubiquitous structural motifs found in natural products and biologically active small molecules. Here, we report an Rh-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes, affording cyclic products in good to excellent yield. Divergent syntheses of α-pyridones and cyclic imidates are accomplished by employing N-phenyl acrylamides and N-tosyl acrylamides as substrates, respectively. Additionally, excellent regioselectivities are achieved when using unsymmetrical alkynes. This electrochemical process is environmentally benign compared to traditional transition metal-catalyzed C–H annulations because it avoids the use of stoichiometric metal oxidants. DFT calculations elucidated the reaction mechanism and origins of substituent-controlled chemoselectivity. The sequential C–H activation and alkyne insertion under rhodium catalysis leads to the seven-membered ring vinyl-rhodium intermediate. This intermediate undergoes either the classic neutral concerted reductive elimination to produce α-pyridones, or the ionic stepwise pathway to produce cyclic imidates. |
format | Online Article Text |
id | pubmed-7876044 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-78760442021-02-24 Divergent rhodium-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes Xing, Yi-Kang Chen, Xin-Ran Yang, Qi-Liang Zhang, Shuo-Qing Guo, Hai-Ming Hong, Xin Mei, Tian-Sheng Nat Commun Article α-Pyridones and α-pyrones are ubiquitous structural motifs found in natural products and biologically active small molecules. Here, we report an Rh-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes, affording cyclic products in good to excellent yield. Divergent syntheses of α-pyridones and cyclic imidates are accomplished by employing N-phenyl acrylamides and N-tosyl acrylamides as substrates, respectively. Additionally, excellent regioselectivities are achieved when using unsymmetrical alkynes. This electrochemical process is environmentally benign compared to traditional transition metal-catalyzed C–H annulations because it avoids the use of stoichiometric metal oxidants. DFT calculations elucidated the reaction mechanism and origins of substituent-controlled chemoselectivity. The sequential C–H activation and alkyne insertion under rhodium catalysis leads to the seven-membered ring vinyl-rhodium intermediate. This intermediate undergoes either the classic neutral concerted reductive elimination to produce α-pyridones, or the ionic stepwise pathway to produce cyclic imidates. Nature Publishing Group UK 2021-02-10 /pmc/articles/PMC7876044/ /pubmed/33568643 http://dx.doi.org/10.1038/s41467-021-21190-8 Text en © The Author(s) 2021 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/. |
spellingShingle | Article Xing, Yi-Kang Chen, Xin-Ran Yang, Qi-Liang Zhang, Shuo-Qing Guo, Hai-Ming Hong, Xin Mei, Tian-Sheng Divergent rhodium-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes |
title | Divergent rhodium-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes |
title_full | Divergent rhodium-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes |
title_fullStr | Divergent rhodium-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes |
title_full_unstemmed | Divergent rhodium-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes |
title_short | Divergent rhodium-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes |
title_sort | divergent rhodium-catalyzed electrochemical vinylic c–h annulation of acrylamides with alkynes |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7876044/ https://www.ncbi.nlm.nih.gov/pubmed/33568643 http://dx.doi.org/10.1038/s41467-021-21190-8 |
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