Changchun Institute of Optics,Fine Mechanics and Physics,CAS
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
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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 |
URL | 查看原文 |
收录类别 | SCI |
语种 | 英语 |
引用统计 | |
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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