Knowledge Management System Of Guangzhou Institute of Energy Conversion, CAS
| Mechanistic study of the ligand controlled regioselectivity in iridium catalyzed C- H borylation of aromatic imines | |
| Liu, Yuhua1; Chen, Jipei1; Zhan, Kangsheng1; Shen, Yiqiang1; Gao, Hui2,3,4; Yao, Lingmin1 | |
| 2018 | |
| Source Publication | RSC ADVANCES
 |
| ISSN | 2046-2069 |
| Volume | 8Issue:62Pages:35453-35460 |
| Corresponding Author | Gao, Hui(gaoh9@gzhmu.edu.cn) ; Yao, Lingmin(emmiyao@163.com) |
| Abstract | 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. |
| DOI | 10.1039/c8ra07886f |
| WOS Keyword | ARENES ; FUNCTIONALIZATION ; DENSITY ; BONDS ; SUBSTITUENTS ; HETEROCYCLES ; CHEMISTRY ; DIBORON |
| Indexed By | SCI |
| Language | 英语 |
| Funding Project | 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 Research Area | Chemistry |
| Funding Organization | 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 |
| WOS Subject | Chemistry, Multidisciplinary |
| WOS ID | WOS:000448348900015 |
| Publisher | ROYAL SOC CHEMISTRY |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.giec.ac.cn/handle/344007/24135 |
| Collection | 中国科学院广州能源研究所 |
| Corresponding Author | Gao, Hui; Yao, Lingmin |
| Affiliation | 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 |
| Recommended Citation 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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