中文版 | English
Title

A Mechanistic Study of the Cobalt(I)-Catalyzed Amination of Aryl Halides: Effects of Metal and Ligand

Author
Corresponding AuthorLi,Xin; Chung,Lung Wa
Publication Years
2022
DOI
Source Title
ISSN
0020-1669
EISSN
1520-510X
Abstract
Transition-metal-catalyzed amination of aryl halides is a useful approach for the synthesis of medicinal compounds, organic functional materials, and agrochemical compounds. A systematic DFT study has been performed to investigate the mechanism of the Co(I)-catalyzed amination of aryl halides by LiN(SiMe3)2 using (PPh3)3CoCl as the precatalyst. Our computational results suggest that the most favorable dissociative concerted C-I activation pathway in a triplet state consists of (a) dissociation of one PPh3 ligand, (b) concerted oxidative addition (OA) of the C-I bond, (c) transmetalation, (d) (optional) dissociation of the second PPh3 ligand, (e) C-N bond-forming reductive elimination (RE), and (f) ligand exchange to regenerate the active species. Comparatively, the associative concerted OA, radical, SH2/SN2, single electron transfer (SET), and σ-bond metathesis pathways should be less favorable due to their higher barriers or unfavorable reaction free energies. The effects of different metals (Rh and Ir) as centers in the catalyst were further examined and found to require higher reaction barriers, due to unfavorable dissociation of their stronger M-PPh3 bonds. These results highlight an advantage of the earth-abundant Co catalysts for the dissociative pathway(s). Overall, our study offers deeper mechanistic insights for the transition-metal-catalyzed amination and guides the design for efficient Co-based catalysts.
URL[Source Record]
Indexed By
Language
English
Important Publications
NI Journal Papers
SUSTech Authorship
Corresponding
WOS Accession No
WOS:000880036600001
ESI Research Field
CHEMISTRY
Scopus EID
2-s2.0-85141736083
Data Source
Scopus
Citation statistics
Cited Times [WOS]:0
Document TypeJournal Article
Identifierhttp://kc.sustech.edu.cn/handle/2SGJ60CL/411869
DepartmentDepartment of Chemistry
深圳格拉布斯研究院
Affiliation
1.School of Chemistry and Chemical Engineering,Harbin Institute of Technology,Harbin,150001,China
2.Shenzhen Grubbs Institute,Department of Chemistry and Guangdong Provincial,Key Laboratory of Catalysis,Southern University of Science and Technology (SUSTech),Shenzhen,518055,China
3.Lab of Computational Chemistry and Drug Design,Key Laboratory of Chemical Genomics,Peking University,Shenzhen Graduate School,Shenzhen,518055,China
First Author AffilicationDepartment of Chemistry;  Shenzhen Grubbs Institute
Corresponding Author AffilicationDepartment of Chemistry;  Shenzhen Grubbs Institute
Recommended Citation
GB/T 7714
Lan,Jialing,Zhang,Tonghuan,Yang,Yuhong,et al. A Mechanistic Study of the Cobalt(I)-Catalyzed Amination of Aryl Halides: Effects of Metal and Ligand[J]. INORGANIC CHEMISTRY,2022.
APA
Lan,Jialing,Zhang,Tonghuan,Yang,Yuhong,Li,Xin,&Chung,Lung Wa.(2022).A Mechanistic Study of the Cobalt(I)-Catalyzed Amination of Aryl Halides: Effects of Metal and Ligand.INORGANIC CHEMISTRY.
MLA
Lan,Jialing,et al."A Mechanistic Study of the Cobalt(I)-Catalyzed Amination of Aryl Halides: Effects of Metal and Ligand".INORGANIC CHEMISTRY (2022).
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