Reactivity of 2-benzylpyridyl lithium toward benzonitrile derivatives: Addition versus elimination
文献类型：期刊论文
| 作者 | Hao, Xiaomin1; Qin, Lu1; Xu, Mali1; Chen, Xia1,2 |
| 刊名 | JOURNAL OF ORGANOMETALLIC CHEMISTRY
 |
| 出版日期 | 2017-12-15 |
| 卷号 | 853页码:168-177 |
| ISSN号 | 0022-328X |
| 关键词 | 2-benzylpyridyl Lithium Nitriles Addition Elimination Bimolecular Coupling Silyl Group Migration |
| DOI | 10.1016/j.jorganchem.2017.10.042 |
| 英文摘要 | This work investigated the reactivity of 2-benzylpyridyl lithium (2-Pyr) C(Ph)(R)Li (R - SiMe3, Li1; R - H, Li2) toward benzonitrile derivatives. Based on the different products, the reaction between lithium salts and nitriles might involve in addition, elimination and bimolecular coupling pathways, respectively. Treatment of Li1 with ArCN (Ar = Ph, p-Tolyl, o-Tolyl, p-OMePh) yielded an addition intermediate pyridyl- 1-aza-allyl-lithium [{(2-Pyr)C(Ph)C(Ar)N(SiMe3)}Li](2) (1, Ar = Ph) and its corresponding hydrolysis product 2-benzylpyridyl-ketone 2-5, respectively, in which the reaction involved in a 1,3-shift of -SiMe3 group to form a dimeric pyridyl-1-aza-allyl-lithium then followed by acidic hydrolysis. The MeOLi elimination reaction between Li2 and p-MeO(C6H4) CN resulted in formation of 4-(2-benzylpyridyl) benzonitrile 6. The reaction of Li2 with p-Me(C6H4) CN in the presence of TMEDA generated a 1: 2 hydrolysis adduct 2-benzylpyridyl-enaminone 7, however, in the absence of TMEDA it afforded a coupling product of bimolecular nitriles, 1-(4-methylphenyl)-2-cyanophenyl-ethanone 8. We speculated the reaction mechanisms in sequence. The crystal structures of 1 and 5-8 were analyzed. (C) 2017 Elsevier B.V. All rights reserved. |
| 语种 | 英语 |
| 出版者 | ELSEVIER SCIENCE SA |
| WOS记录号 | WOS:000417654800021 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/45287]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Chen, Xia |
| 作者单位 | 1.Shanxi Univ, Sch Chem & Chem Engn, Taiyuan 030006, Peoples R China 2.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Jilin, Peoples R China |
| 推荐引用方式 GB/T 7714 | Hao, Xiaomin,Qin, Lu,Xu, Mali,et al. Reactivity of 2-benzylpyridyl lithium toward benzonitrile derivatives: Addition versus elimination[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2017,853:168-177. |
| APA | Hao, Xiaomin,Qin, Lu,Xu, Mali,&Chen, Xia.(2017).Reactivity of 2-benzylpyridyl lithium toward benzonitrile derivatives: Addition versus elimination.JOURNAL OF ORGANOMETALLIC CHEMISTRY,853,168-177. |
| MLA | Hao, Xiaomin,et al."Reactivity of 2-benzylpyridyl lithium toward benzonitrile derivatives: Addition versus elimination".JOURNAL OF ORGANOMETALLIC CHEMISTRY 853(2017):168-177. |
入库方式： OAI收割
来源：化学研究所
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