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Nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides

The catalytic generation of homoenolates and their higher homologues has been a long-standing challenge. Like the generation of transition metal enolates, which have been used to great affect in synthesis and medicinal chemistries, homoenolates and their higher homologues have much potential, albeit...

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Autores principales: Lin, Tingzhi, Gu, Yuanyun, Qian, Pengcheng, Guan, Haixing, Walsh, Patrick J., Mao, Jianyou
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7648641/
https://www.ncbi.nlm.nih.gov/pubmed/33159055
http://dx.doi.org/10.1038/s41467-020-19194-x
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author Lin, Tingzhi
Gu, Yuanyun
Qian, Pengcheng
Guan, Haixing
Walsh, Patrick J.
Mao, Jianyou
author_facet Lin, Tingzhi
Gu, Yuanyun
Qian, Pengcheng
Guan, Haixing
Walsh, Patrick J.
Mao, Jianyou
author_sort Lin, Tingzhi
collection PubMed
description The catalytic generation of homoenolates and their higher homologues has been a long-standing challenge. Like the generation of transition metal enolates, which have been used to great affect in synthesis and medicinal chemistries, homoenolates and their higher homologues have much potential, albeit largely unrealized. Herein, a nickel-catalyzed generation of homoenolates, and their higher homologues, via decarbonylation of readily available cyclic anhydrides has been developed. The utility of nickel-bound homoenolates and their higher homologues is demonstrated by cross-coupling with unactivated alkyl bromides, generating a diverse array of aliphatic acids. A broad range of functional groups is tolerated. Preliminary mechanistic studies demonstrate that: (1) oxidative addition of anhydrides by the catalyst is faster than oxidative addition of alkyl bromides; (2) nickel bound metallocycles are involved in this transformation and (3) the catalyst undergoes a single electron transfer (SET) process with the alkyl bromide.
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spelling pubmed-76486412020-11-10 Nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides Lin, Tingzhi Gu, Yuanyun Qian, Pengcheng Guan, Haixing Walsh, Patrick J. Mao, Jianyou Nat Commun Article The catalytic generation of homoenolates and their higher homologues has been a long-standing challenge. Like the generation of transition metal enolates, which have been used to great affect in synthesis and medicinal chemistries, homoenolates and their higher homologues have much potential, albeit largely unrealized. Herein, a nickel-catalyzed generation of homoenolates, and their higher homologues, via decarbonylation of readily available cyclic anhydrides has been developed. The utility of nickel-bound homoenolates and their higher homologues is demonstrated by cross-coupling with unactivated alkyl bromides, generating a diverse array of aliphatic acids. A broad range of functional groups is tolerated. Preliminary mechanistic studies demonstrate that: (1) oxidative addition of anhydrides by the catalyst is faster than oxidative addition of alkyl bromides; (2) nickel bound metallocycles are involved in this transformation and (3) the catalyst undergoes a single electron transfer (SET) process with the alkyl bromide. Nature Publishing Group UK 2020-11-06 /pmc/articles/PMC7648641/ /pubmed/33159055 http://dx.doi.org/10.1038/s41467-020-19194-x 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
Lin, Tingzhi
Gu, Yuanyun
Qian, Pengcheng
Guan, Haixing
Walsh, Patrick J.
Mao, Jianyou
Nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides
title Nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides
title_full Nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides
title_fullStr Nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides
title_full_unstemmed Nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides
title_short Nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides
title_sort nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7648641/
https://www.ncbi.nlm.nih.gov/pubmed/33159055
http://dx.doi.org/10.1038/s41467-020-19194-x
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