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

Xu Luo, Dali Yang, Xiaoqian He, Shengchun Wang, Dongchao Zhang, Jiaxin Xu, Chih-Wen Pao, Jeng-Lung Chen, Jyh-Fu Lee, Hengjiang Cong, Yu Lan, Hesham Alhumade, Janine Cossy (), Ruopeng Bai (), Yi-Hung Chen (), Hong Yi () and Aiwen Lei ()
Additional contact information
Xu Luo: Wuhan University
Dali Yang: Wuhan University
Xiaoqian He: Chongqing University
Shengchun Wang: Wuhan University
Dongchao Zhang: Wuhan University
Jiaxin Xu: Wuhan University
Chih-Wen Pao: National Synchrotron Radiation Research Center
Jeng-Lung Chen: National Synchrotron Radiation Research Center
Jyh-Fu Lee: National Synchrotron Radiation Research Center
Hengjiang Cong: Wuhan University
Yu Lan: Chongqing University
Hesham Alhumade: King Abdulaziz University
Janine Cossy: PSL University
Ruopeng Bai: Chongqing University
Yi-Hung Chen: Wuhan University
Hong Yi: Wuhan University
Aiwen Lei: Wuhan University

Nature Communications, 2023, vol. 14, issue 1, 1-10

Abstract: Abstract 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 CoCl2bpy2 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.

Date: 2023
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DOI: 10.1038/s41467-023-40269-y

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