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Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity
The C-C σ-bond activation of unstrained cycloketones represents an ingenious and advanced technique in synthetic chemistry, but it remains a challenging area which has been largely underexplored. Herein we report an efficient strategy for the direct C-C cleavage of cyclohexanones and cyclopentanones...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6997357/ https://www.ncbi.nlm.nih.gov/pubmed/32015335 http://dx.doi.org/10.1038/s41467-020-14435-5 |
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author | Wang, Mingyang Li, Man Yang, Shan Xue, Xiao-Song Wu, Xinxin Zhu, Chen |
author_facet | Wang, Mingyang Li, Man Yang, Shan Xue, Xiao-Song Wu, Xinxin Zhu, Chen |
author_sort | Wang, Mingyang |
collection | PubMed |
description | The C-C σ-bond activation of unstrained cycloketones represents an ingenious and advanced technique in synthetic chemistry, but it remains a challenging area which has been largely underexplored. Herein we report an efficient strategy for the direct C-C cleavage of cyclohexanones and cyclopentanones. The cyclic C-C σ-bond is readily cleaved under mild conditions with the aid of an in situ formed side-chain aryl radical. Density functional theory calculations are carried out to shed light on the unusual regioselectivity of C-C bond cleavage. The reaction affords a variety of structurally diverse 3-coumaranones and indanones that widely exist in natural products and bioactive molecules, illustrating the synthetic value of this method. |
format | Online Article Text |
id | pubmed-6997357 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-69973572020-02-05 Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity Wang, Mingyang Li, Man Yang, Shan Xue, Xiao-Song Wu, Xinxin Zhu, Chen Nat Commun Article The C-C σ-bond activation of unstrained cycloketones represents an ingenious and advanced technique in synthetic chemistry, but it remains a challenging area which has been largely underexplored. Herein we report an efficient strategy for the direct C-C cleavage of cyclohexanones and cyclopentanones. The cyclic C-C σ-bond is readily cleaved under mild conditions with the aid of an in situ formed side-chain aryl radical. Density functional theory calculations are carried out to shed light on the unusual regioselectivity of C-C bond cleavage. The reaction affords a variety of structurally diverse 3-coumaranones and indanones that widely exist in natural products and bioactive molecules, illustrating the synthetic value of this method. Nature Publishing Group UK 2020-02-03 /pmc/articles/PMC6997357/ /pubmed/32015335 http://dx.doi.org/10.1038/s41467-020-14435-5 Text en © The Author(s) 2020 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 Wang, Mingyang Li, Man Yang, Shan Xue, Xiao-Song Wu, Xinxin Zhu, Chen Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity |
title | Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity |
title_full | Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity |
title_fullStr | Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity |
title_full_unstemmed | Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity |
title_short | Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity |
title_sort | radical-mediated c-c cleavage of unstrained cycloketones and dft study for unusual regioselectivity |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6997357/ https://www.ncbi.nlm.nih.gov/pubmed/32015335 http://dx.doi.org/10.1038/s41467-020-14435-5 |
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