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...

Descripción completa

Detalles Bibliográficos
Autores principales: Guo, Lin, Srimontree, Watchara, Zhu, Chen, Maity, Bholanath, Liu, Xiangqian, Cavallo, Luigi, Rueping, Magnus
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2019
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
_version_ 1783414675130548224
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
work_keys_str_mv AT guolin nickelcatalyzedsuzukimiyauracrosscouplingsofaldehydes
AT srimontreewatchara nickelcatalyzedsuzukimiyauracrosscouplingsofaldehydes
AT zhuchen nickelcatalyzedsuzukimiyauracrosscouplingsofaldehydes
AT maitybholanath nickelcatalyzedsuzukimiyauracrosscouplingsofaldehydes
AT liuxiangqian nickelcatalyzedsuzukimiyauracrosscouplingsofaldehydes
AT cavalloluigi nickelcatalyzedsuzukimiyauracrosscouplingsofaldehydes
AT ruepingmagnus nickelcatalyzedsuzukimiyauracrosscouplingsofaldehydes