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
发表期刊	Organic Chemistry Frontiers
ISSN	2052-4129
卷号	7 期号:16 页码:2168-2178
摘要	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
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收录类别	SCI
语种	英语
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文献类型	期刊论文
条目标识符	http://ir.ciomp.ac.cn/handle/181722/64953
专题	中国科学院长春光学精密机械与物理研究所
推荐引用方式 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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