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Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling

Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Herein, an on-cycle mechanism is reported for CoCl(2)bpy(2) catalyzed Negishi-type cross-coupling. A full catalytic cycle o...

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Autores principales: Luo, Xu, Yang, Dali, He, Xiaoqian, Wang, Shengchun, Zhang, Dongchao, Xu, Jiaxin, Pao, Chih-Wen, Chen, Jeng-Lung, Lee, Jyh-Fu, Cong, Hengjiang, Lan, Yu, Alhumade, Hesham, Cossy, Janine, Bai, Ruopeng, Chen, Yi-Hung, Yi, Hong, Lei, Aiwen
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10397345/
https://www.ncbi.nlm.nih.gov/pubmed/37532729
http://dx.doi.org/10.1038/s41467-023-40269-y
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author Luo, Xu
Yang, Dali
He, Xiaoqian
Wang, Shengchun
Zhang, Dongchao
Xu, Jiaxin
Pao, Chih-Wen
Chen, Jeng-Lung
Lee, Jyh-Fu
Cong, Hengjiang
Lan, Yu
Alhumade, Hesham
Cossy, Janine
Bai, Ruopeng
Chen, Yi-Hung
Yi, Hong
Lei, Aiwen
author_facet Luo, Xu
Yang, Dali
He, Xiaoqian
Wang, Shengchun
Zhang, Dongchao
Xu, Jiaxin
Pao, Chih-Wen
Chen, Jeng-Lung
Lee, Jyh-Fu
Cong, Hengjiang
Lan, Yu
Alhumade, Hesham
Cossy, Janine
Bai, Ruopeng
Chen, Yi-Hung
Yi, Hong
Lei, Aiwen
author_sort Luo, Xu
collection PubMed
description Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Herein, an on-cycle mechanism is reported for CoCl(2)bpy(2) catalyzed Negishi-type cross-coupling. A full catalytic cycle of this kind of reaction was elucidated by multiple spectroscopic studies. The solvent and ligand were found to be essential for the generation of catalytic active Co(I) species, among which acetonitrile and bipyridine ligand are resistant to the disproportionation events of Co(I). Investigations, based on Quick-X-Ray Absorption Fine Structure (Q-XAFS) spectroscopy, Electron Paramagnetic Resonance (EPR), IR allied with DFT calculations, allow comprehensive mechanistic insights that establish the structural information of the catalytic active cobalt species along with the whole catalytic Co(I)/Co(III) cycle. Moreover, the acetonitrile and bipyridine system can be further extended to the acylation, allylation, and benzylation of aryl zinc reagents, which present a broad substrate scope with a catalytic amount of Co salt. Overall, this work provides a basic mechanistic perspective for designing cobalt-catalyzed cross-coupling reactions.
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spelling pubmed-103973452023-08-04 Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling Luo, Xu Yang, Dali He, Xiaoqian Wang, Shengchun Zhang, Dongchao Xu, Jiaxin Pao, Chih-Wen Chen, Jeng-Lung Lee, Jyh-Fu Cong, Hengjiang Lan, Yu Alhumade, Hesham Cossy, Janine Bai, Ruopeng Chen, Yi-Hung Yi, Hong Lei, Aiwen Nat Commun Article Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Herein, an on-cycle mechanism is reported for CoCl(2)bpy(2) catalyzed Negishi-type cross-coupling. A full catalytic cycle of this kind of reaction was elucidated by multiple spectroscopic studies. The solvent and ligand were found to be essential for the generation of catalytic active Co(I) species, among which acetonitrile and bipyridine ligand are resistant to the disproportionation events of Co(I). Investigations, based on Quick-X-Ray Absorption Fine Structure (Q-XAFS) spectroscopy, Electron Paramagnetic Resonance (EPR), IR allied with DFT calculations, allow comprehensive mechanistic insights that establish the structural information of the catalytic active cobalt species along with the whole catalytic Co(I)/Co(III) cycle. Moreover, the acetonitrile and bipyridine system can be further extended to the acylation, allylation, and benzylation of aryl zinc reagents, which present a broad substrate scope with a catalytic amount of Co salt. Overall, this work provides a basic mechanistic perspective for designing cobalt-catalyzed cross-coupling reactions. Nature Publishing Group UK 2023-08-02 /pmc/articles/PMC10397345/ /pubmed/37532729 http://dx.doi.org/10.1038/s41467-023-40269-y Text en © The Author(s) 2023 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 licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence 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 licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Luo, Xu
Yang, Dali
He, Xiaoqian
Wang, Shengchun
Zhang, Dongchao
Xu, Jiaxin
Pao, Chih-Wen
Chen, Jeng-Lung
Lee, Jyh-Fu
Cong, Hengjiang
Lan, Yu
Alhumade, Hesham
Cossy, Janine
Bai, Ruopeng
Chen, Yi-Hung
Yi, Hong
Lei, Aiwen
Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling
title Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling
title_full Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling
title_fullStr Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling
title_full_unstemmed Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling
title_short Valve turning towards on-cycle in cobalt-catalyzed Negishi-type cross-coupling
title_sort valve turning towards on-cycle in cobalt-catalyzed negishi-type cross-coupling
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10397345/
https://www.ncbi.nlm.nih.gov/pubmed/37532729
http://dx.doi.org/10.1038/s41467-023-40269-y
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