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Mechanistic study of the ligand controlled regioselectivity in iridium catalyzed C- H borylation of aromatic imines

文献类型：期刊论文

作者Liu, Yuhua1; Chen, Jipei1; Zhan, Kangsheng1; Shen, Yiqiang1; Gao, Hui2,3,4; Yao, Lingmin1
刊名RSC ADVANCES
出版日期2018
卷号8期号:62页码:35453-35460
ISSN号2046-2069
DOI10.1039/c8ra07886f
通讯作者Gao, Hui(gaoh9@gzhmu.edu.cn) ; Yao, Lingmin(emmiyao@163.com)
英文摘要As a major challenge in C-H borylation, how to control the selectivity has attracted lots of attention, however, the related mechanistic information still needs to be uncovered. Herein, density functional theory (DFT) has been used to study the mechanism for the ligand controlled regioselectivity in the iridium-catalyzed C-H borylation of aromatic imines, which is inspired by experimental observations (R. Bisht, B. Chattopadhyay, J. Am. Chem. Soc., 2016, 138, 84-87). The proposed Ir(i)-Ir(iii) catalytic cycle includes (i) the oxidative addition of the C-H bond to iridium(i); (ii) the reductive elimination of a C-B bond; (iii) the oxidative addition of B(2)pin(2) to an iridium(i) hydride complex; and (iv) the reductive elimination of a B-H bond. The oxidative addition of a C-H bond to the iridium center is the determining step. For the ligand AQ, ortho-selectivity is proposed to be attributed to the decreased steric hindrance and increased electron donating effect of AQ (8-aminoquinoline) which promotes proton-transfer in the ortho-transition state of C-H activation. While, for the TMP ligand, the steric repulsion between the TMP (4,5,7,8-tetramethyl-1, 10-phenanthroline) ligand and the ortho-substituted imine hinders the ortho C-H activation and favors meta borylation. Our calculations provide insights into further ligand design to achieve different regioselective borylation of aromatics. Guided by the results, the regioselectivity in the borylation of aromatics may be achieved by accordingly modifying the electronic and steric substituents of the ligand.
WOS关键词ARENES ; FUNCTIONALIZATION ; DENSITY ; BONDS ; SUBSTITUENTS ; HETEROCYCLES ; CHEMISTRY ; DIBORON
资助项目Natural Science Foundation of Guangdong Province[2017A030313020] ; Natural Science Foundation of Guangdong Province[2018A030313274] ; National Natural Science Foundation of China[11604059] ; Scientific Research Project of Guangzhou Municipal Colleges and Universities[1201630455] ; Guangzhou University's Training Program for Excellent New-recruited Doctors[YB201715] ; Priority Academic Program Development of Jiangsu Higher Education Institutions, China
WOS研究方向Chemistry
语种英语
WOS记录号WOS:000448348900015
出版者ROYAL SOC CHEMISTRY
资助机构Natural Science Foundation of Guangdong Province ; National Natural Science Foundation of China ; Scientific Research Project of Guangzhou Municipal Colleges and Universities ; Guangzhou University's Training Program for Excellent New-recruited Doctors ; Priority Academic Program Development of Jiangsu Higher Education Institutions, China
源URL[http://ir.giec.ac.cn/handle/344007/24134]  
专题中国科学院广州能源研究所
通讯作者Gao, Hui; Yao, Lingmin
作者单位1.Guangzhou Univ, Sch Phys & Elect Engn, Guangzhou 510006, Guangdong, Peoples R China
2.Guangzhou Med Univ, Key Lab Mol Target & Clin Pharmacol, Sch Pharmaceut Sci, Guangzhou 511436, Guangdong, Peoples R China
3.Guangzhou Med Univ, Affiliated Hosp 5, Guangzhou 511436, Guangdong, Peoples R China
4.Chinese Acad Sci, Guangzhou Inst Energy Convers, Guangzhou 510640, Guangdong, Peoples R China
推荐引用方式
GB/T 7714		 Liu, Yuhua,Chen, Jipei,Zhan, Kangsheng,et al. Mechanistic study of the ligand controlled regioselectivity in iridium catalyzed C- H borylation of aromatic imines[J]. RSC ADVANCES,2018,8(62):35453-35460.
APA Liu, Yuhua,Chen, Jipei,Zhan, Kangsheng,Shen, Yiqiang,Gao, Hui,&Yao, Lingmin.(2018).Mechanistic study of the ligand controlled regioselectivity in iridium catalyzed C- H borylation of aromatic imines.RSC ADVANCES,8(62),35453-35460.
MLA Liu, Yuhua,et al."Mechanistic study of the ligand controlled regioselectivity in iridium catalyzed C- H borylation of aromatic imines".RSC ADVANCES 8.62(2018):35453-35460.

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来源：广州能源研究所

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