Nickel-catalyzed Suzuki–Miyaura cross-couplings of aldehydes
Transition-metal-catalyzed cross-couplings have been extensively used in the pharmaceutical and agrochemical industries for the construction of diverse C–C bonds. Conventional cross-coupling reactions require reactive electrophilic coupling partners, such as organohalides or sulfonates, which are no...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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Nature Publishing Group UK
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6488620/ https://www.ncbi.nlm.nih.gov/pubmed/31036821 http://dx.doi.org/10.1038/s41467-019-09766-x |
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author | Guo, Lin Srimontree, Watchara Zhu, Chen Maity, Bholanath Liu, Xiangqian Cavallo, Luigi Rueping, Magnus |
author_facet | Guo, Lin Srimontree, Watchara Zhu, Chen Maity, Bholanath Liu, Xiangqian Cavallo, Luigi Rueping, Magnus |
author_sort | Guo, Lin |
collection | PubMed |
description | Transition-metal-catalyzed cross-couplings have been extensively used in the pharmaceutical and agrochemical industries for the construction of diverse C–C bonds. Conventional cross-coupling reactions require reactive electrophilic coupling partners, such as organohalides or sulfonates, which are not environmentally friendly and not naturally abundant. Another disadvantage associated with these transformations is the need for an exogenous base to facilitate the key transmetalation step, and this reagent inevitably induces side reactions and limits the substrate scope. Here, we report an unconventional Suzuki-type approach to the synthesis of biaryls, through nickel-catalyzed deformylative cross coupling of aldehydes with organoboron reagents under base-free conditions. The transformation tolerates structurally diverse (hetero)aryl substituents on both coupling partners and shows high reactivity and excellent functional group tolerance. Furthermore, the protocol was carried out on gram scale and successfully applied to the functionalization of complex biologically active molecules. Mechanistic investigations support a catalytic cycle involving the oxidative addition of the nickel into the aldehyde C(acyl)–H bond with subsequent hydride transfer, transmetalation, decarbonylation and reductive elimination processes. |
format | Online Article Text |
id | pubmed-6488620 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-64886202019-05-01 Nickel-catalyzed Suzuki–Miyaura cross-couplings of aldehydes Guo, Lin Srimontree, Watchara Zhu, Chen Maity, Bholanath Liu, Xiangqian Cavallo, Luigi Rueping, Magnus Nat Commun Article Transition-metal-catalyzed cross-couplings have been extensively used in the pharmaceutical and agrochemical industries for the construction of diverse C–C bonds. Conventional cross-coupling reactions require reactive electrophilic coupling partners, such as organohalides or sulfonates, which are not environmentally friendly and not naturally abundant. Another disadvantage associated with these transformations is the need for an exogenous base to facilitate the key transmetalation step, and this reagent inevitably induces side reactions and limits the substrate scope. Here, we report an unconventional Suzuki-type approach to the synthesis of biaryls, through nickel-catalyzed deformylative cross coupling of aldehydes with organoboron reagents under base-free conditions. The transformation tolerates structurally diverse (hetero)aryl substituents on both coupling partners and shows high reactivity and excellent functional group tolerance. Furthermore, the protocol was carried out on gram scale and successfully applied to the functionalization of complex biologically active molecules. Mechanistic investigations support a catalytic cycle involving the oxidative addition of the nickel into the aldehyde C(acyl)–H bond with subsequent hydride transfer, transmetalation, decarbonylation and reductive elimination processes. Nature Publishing Group UK 2019-04-29 /pmc/articles/PMC6488620/ /pubmed/31036821 http://dx.doi.org/10.1038/s41467-019-09766-x Text en © The Author(s) 2019 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 Guo, Lin Srimontree, Watchara Zhu, Chen Maity, Bholanath Liu, Xiangqian Cavallo, Luigi Rueping, Magnus Nickel-catalyzed Suzuki–Miyaura cross-couplings of aldehydes |
title | Nickel-catalyzed Suzuki–Miyaura cross-couplings of aldehydes |
title_full | Nickel-catalyzed Suzuki–Miyaura cross-couplings of aldehydes |
title_fullStr | Nickel-catalyzed Suzuki–Miyaura cross-couplings of aldehydes |
title_full_unstemmed | Nickel-catalyzed Suzuki–Miyaura cross-couplings of aldehydes |
title_short | Nickel-catalyzed Suzuki–Miyaura cross-couplings of aldehydes |
title_sort | nickel-catalyzed suzuki–miyaura cross-couplings of aldehydes |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6488620/ https://www.ncbi.nlm.nih.gov/pubmed/31036821 http://dx.doi.org/10.1038/s41467-019-09766-x |
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