Theoretical mechanistic study of metallaphotoredox catalysis: C-N cross-coupling via Ni(II)-mediated sigma-bond metathesis

doi:10.1039/d0qo00458h

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	Theoretical mechanistic study of metallaphotoredox catalysis: C-N cross-coupling via Ni(II)-mediated sigma-bond metathesis
	R. H. Li,B. Zhu,S. Wang,Y. Geng,L. K. Yan,Z. M. Su,L. S. Yao,R. L. Zhong and W. Guan
	2020
Source Publication	Organic Chemistry Frontiers
ISSN	2052-4129
Volume	7 Issue:16 Pages:2168-2178
Abstract	The C-N cross-coupling reaction has been achieved by photoredox-mediated iridium/nickel dual catalysis, but its mechanism is still controversial in these reactions. A theoretical mechanistic study of the highly chemoselective C-N cross-coupling of pyrrolidine with 4-bromobenzotrifluoride has been performed using density functional theory (DFT) calculations. The oxidation state modulation mechanisms initiated by reductive quenching and oxidative quenching are unfavourable due to the mismatched redox potentials and slow electron transfer rates. In contrast, a radical mechanism merging reductive quenching (Ir-III-*Ir-III-Ir-II-Ir-III) and nickel catalytic cycles (Ni-II-Ni-III-Ni-II-Ni-II) is favourable. It consists of four major processes: exogenous base triggered successive single electron transfer (SET) and hydrogen atom transfer (HAT) to generate a nitrogen-centred radical, radical capture by nickel(II) dibromide, SET to regenerate iridium(III), and the rate-determining sigma-bond metathesis to achieve the C-N cross-coupling. Furthermore, the suppression effect caused by alpha-substitution of pyrrolidine on the reaction is dominantly attributed to the steric effect rather than the electronic effect. Unlike the C-N cross-coupling, the concerted s-bond metathesis involving nickel(II) is inapplicable for the C-O and C-S cross-couplings due to the high energy barriers. This study is expected to provide new mechanistic insights into metallaphotoredox-catalysed C-N cross-coupling.
DOI	10.1039/d0qo00458h
URL	查看原文
Indexed By	SCI
Language	英语
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Document Type	期刊论文
Identifier	http://ir.ciomp.ac.cn/handle/181722/64953
Collection	中国科学院长春光学精密机械与物理研究所
Recommended Citation GB/T 7714	R. H. Li,B. Zhu,S. Wang,Y. Geng,L. K. Yan,Z. M. Su,L. S. Yao,R. L. Zhong and W. Guan. Theoretical mechanistic study of metallaphotoredox catalysis: C-N cross-coupling via Ni(II)-mediated sigma-bond metathesis[J]. Organic Chemistry Frontiers,2020,7(16):2168-2178.
APA	R. H. Li,B. Zhu,S. Wang,Y. Geng,L. K. Yan,Z. M. Su,L. S. Yao,R. L. Zhong and W. Guan.(2020).Theoretical mechanistic study of metallaphotoredox catalysis: C-N cross-coupling via Ni(II)-mediated sigma-bond metathesis.Organic Chemistry Frontiers,7(16),2168-2178.
MLA	R. H. Li,B. Zhu,S. Wang,Y. Geng,L. K. Yan,Z. M. Su,L. S. Yao,R. L. Zhong and W. Guan."Theoretical mechanistic study of metallaphotoredox catalysis: C-N cross-coupling via Ni(II)-mediated sigma-bond metathesis".Organic Chemistry Frontiers 7.16(2020):2168-2178.

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中国科学院长春光学精密机械与物理研究所