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Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage
The cleavage and formation of carbon−carbon bonds have emerged as powerful tools for structural modifications in organic synthesis. Although transition−metal−catalyzed decarbonylation of unstrained diaryl ketones provides a viable protocol to construct biaryl structures, the use of expensive catalys...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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Nature Publishing Group UK
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8979990/ https://www.ncbi.nlm.nih.gov/pubmed/35379809 http://dx.doi.org/10.1038/s41467-022-29327-z |
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author | Cao, Dawei Ataya, Mohamad Chen, Zhangpei Zeng, Huiying Peng, Yong Khaliullin, Rustam Z. Li, Chao-Jun |
author_facet | Cao, Dawei Ataya, Mohamad Chen, Zhangpei Zeng, Huiying Peng, Yong Khaliullin, Rustam Z. Li, Chao-Jun |
author_sort | Cao, Dawei |
collection | PubMed |
description | The cleavage and formation of carbon−carbon bonds have emerged as powerful tools for structural modifications in organic synthesis. Although transition−metal−catalyzed decarbonylation of unstrained diaryl ketones provides a viable protocol to construct biaryl structures, the use of expensive catalyst and high temperature (>140 (o)C) have greatly limited their universal applicability. Moreover, the direct activation of two inert C − C bonds in diaryl ketones without the assistance of metal catalyst has been a great challenge due to the inherent stability of C − C bonds (nonpolar, thermo-dynamically stable, and kinetically inert). Here we report an efficient light-driven transition-metal-free strategy for decarbonylation of unstrained diaryl ketones to construct biaryl compounds through dual inert C − C bonds cleavage. This reaction featured mild reaction conditions, easy-to-handle reactants and reagents, and excellent functional groups tolerance. The mechanistic investigation and DFT calculation suggest that this strategy proceeds through the formation of dioxy radical intermediate via a single-electron-transfer (SET) process between photo-excited diaryl ketone and DBU mediated by DMSO, followed by removal of CO(2) to construct biaryl compounds. |
format | Online Article Text |
id | pubmed-8979990 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-89799902022-04-20 Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage Cao, Dawei Ataya, Mohamad Chen, Zhangpei Zeng, Huiying Peng, Yong Khaliullin, Rustam Z. Li, Chao-Jun Nat Commun Article The cleavage and formation of carbon−carbon bonds have emerged as powerful tools for structural modifications in organic synthesis. Although transition−metal−catalyzed decarbonylation of unstrained diaryl ketones provides a viable protocol to construct biaryl structures, the use of expensive catalyst and high temperature (>140 (o)C) have greatly limited their universal applicability. Moreover, the direct activation of two inert C − C bonds in diaryl ketones without the assistance of metal catalyst has been a great challenge due to the inherent stability of C − C bonds (nonpolar, thermo-dynamically stable, and kinetically inert). Here we report an efficient light-driven transition-metal-free strategy for decarbonylation of unstrained diaryl ketones to construct biaryl compounds through dual inert C − C bonds cleavage. This reaction featured mild reaction conditions, easy-to-handle reactants and reagents, and excellent functional groups tolerance. The mechanistic investigation and DFT calculation suggest that this strategy proceeds through the formation of dioxy radical intermediate via a single-electron-transfer (SET) process between photo-excited diaryl ketone and DBU mediated by DMSO, followed by removal of CO(2) to construct biaryl compounds. Nature Publishing Group UK 2022-04-04 /pmc/articles/PMC8979990/ /pubmed/35379809 http://dx.doi.org/10.1038/s41467-022-29327-z 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 Cao, Dawei Ataya, Mohamad Chen, Zhangpei Zeng, Huiying Peng, Yong Khaliullin, Rustam Z. Li, Chao-Jun Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage |
title | Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage |
title_full | Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage |
title_fullStr | Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage |
title_full_unstemmed | Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage |
title_short | Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage |
title_sort | light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual c–c bond cleavage |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8979990/ https://www.ncbi.nlm.nih.gov/pubmed/35379809 http://dx.doi.org/10.1038/s41467-022-29327-z |
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