Regioselectivity and Mechanism of Synthesizing N-Substituted 2-Pyridones and 2-Substituted Pyridines via Metal-Free C-O and C-N Bond-Cleaving of Oxazoline[3,2-a]pyridiniums
文献类型：期刊论文
| 作者 | Li, Bo2,5; Xue, Susu6; Yang, Yang2,7; Feng, Jia1; Liu, Peng2; Zhang, Yong2; Zhu, Jianming2; Xu, Zhijian2 ; Hall, Adrian4; Zhao, Bo6
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| 刊名 | SCIENTIFIC REPORTS
 |
| 出版日期 | 2017-01-25 |
| 卷号 | 7 |
| ISSN号 | 2045-2322 |
| DOI | 10.1038/srep41287 |
| 文献子类 | Article |
| 英文摘要 | Novel intermediate oxazoline[3,2-a] pyridiniums were facilely prepared from 2-(2,2-dimethoxyethoxy)pyridines via acid promoted intramolecular cyclization. Sequentially, the quaternary ammonium salts were treated with different nucleophiles for performing regioselective metal-free C-O and C-N bond-cleaving to afford prevalent heterocyclic structures of N-substituted pyridones and 2-substituted pyridines. The reaction mechanism and regioselectivity were then systematically explored by quantum chemistry calculations at B3LYP/6-31 g(d) level. The calculated free energy barrier of the reactions revealed that aniline and aliphatic amines (e.g., methylamine) prefer to attack C8 of intermediate 4a, affording N-substituted pyridones, while phenylmethanamine, 2-phenylethan-1-amine and 3-phenylpropan-1-amine favor to attack C2 of the intermediate to form 2-substituted pyridines. With the optimized geometries of the transition states, we found that the aromatic ring of the phenyl aliphatic amines may form cation-pi interaction with the pyridinium of the intermediates, which could stabilize the transition states and facilitate the formation of 2-substituted pyridines. |
| WOS关键词 | REARRANGEMENT ; DISCOVERY ; AMINATION ; REGIO |
| 资助项目 | National Natural Science Foundation[81273435] ; National Natural Science Foundation[81302699] ; National Natural Science Foundation[81573350] ; Natural Science Foundation of Shanghai, China[14ZR1447800] ; State Key Laboratory of Natural and Biomimetic Drugs[K20150205] |
| WOS研究方向 | Science & Technology - Other Topics |
| 语种 | 英语 |
| WOS记录号 | WOS:000392648800001 |
| 出版者 | NATURE PUBLISHING GROUP |
| 源URL | [http://119.78.100.183/handle/2S10ELR8/275669]  |
| 专题 | 药物发现与设计中心 |
| 通讯作者 | Zhao, Bo; Shi, Jiye; Zhu, Weiliang |
| 作者单位 | 1.Univ Sci & Technol China, Nano Sci & Technol Inst, 166 Renai Rd, Suzhou 215123, Peoples R China; 2.Chinese Acad Sci, Shanghai Inst Mat Med, Drug Discovery & Design Ctr, Key Lab Receptor Res, 555 Zuchongzhi Rd, Shanghai 201203, Peoples R China; 3.Univ Oxford, Kellogg Coll, 60-62 Banbury Rd, Oxford OX2 6PN, England 4.UCB Biopharma SPRL, Chemin Foriest, Braine Lalleu, Belgium; 5.Peking Univ, State Key Lab Nat & Biomimet Drugs, 38 Xueyuan Rd, Beijing 100191, Peoples R China; 6.Nanjing Normal Univ, Coll Chem & Environm Sci, 1 Wenyuan Rd, Nanjing 210097, Jiangsu, Peoples R China; 7.Univ Chinese Acad Sci, 19A Yuquan Rd, Beijing 100049, Peoples R China; |
| 推荐引用方式 GB/T 7714 | Li, Bo,Xue, Susu,Yang, Yang,et al. Regioselectivity and Mechanism of Synthesizing N-Substituted 2-Pyridones and 2-Substituted Pyridines via Metal-Free C-O and C-N Bond-Cleaving of Oxazoline[3,2-a]pyridiniums[J]. SCIENTIFIC REPORTS,2017,7. |
| APA | Li, Bo.,Xue, Susu.,Yang, Yang.,Feng, Jia.,Liu, Peng.,...&Zhu, Weiliang.(2017).Regioselectivity and Mechanism of Synthesizing N-Substituted 2-Pyridones and 2-Substituted Pyridines via Metal-Free C-O and C-N Bond-Cleaving of Oxazoline[3,2-a]pyridiniums.SCIENTIFIC REPORTS,7. |
| MLA | Li, Bo,et al."Regioselectivity and Mechanism of Synthesizing N-Substituted 2-Pyridones and 2-Substituted Pyridines via Metal-Free C-O and C-N Bond-Cleaving of Oxazoline[3,2-a]pyridiniums".SCIENTIFIC REPORTS 7(2017). |
入库方式： OAI收割
来源：上海药物研究所
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