ZnI2/NEt3-Catalyzed Cycloaddition of CO2 with Propargylic Alcohols: Computational Study on Mechanism
文献类型：期刊论文
| 作者 | Ma, Jun1 ; Lu, Lu1,2; Mei, Qingqing1; Zhu, Qinggong1; Hu, Jiayin1; Han, Buxing1,2
|
| 刊名 | CHEMCATCHEM
 |
| 出版日期 | 2017-11-09 |
| 卷号 | 9期号:21页码:4090-4097 |
| ISSN号 | 1867-3880 |
| 关键词 | Carbon Dioxide Fixation Cycloaddion Density Functional Calculations Reaction Mechanism Zinc |
| DOI | 10.1002/cctc.201700771 |
| 英文摘要 | The ZnI2(NEt3)/NEt3-catalyzed cycloaddition of CO2 with propargylic alcohols to alpha-alkylidene cyclic carbonates was studied by DFT calculations for the first time to explore the detailed reaction mechanism. By comparing the distinct CO2-activated and OH-activated pathways as well as the solvent effects of reactants and products, a complete picture of the metal-salt/base-catalyzed mechanism is provided, which involves four steps: deprotonation of propargylic alcohol, CO2 electrophilic attack, concerted metalation and intramolecular cyclization, and protonation to form the cyclic carbonates. With the polar solvent effects of reactants or products, the third step is the rate-determining step. The role of ZnII is activating the hydroxyl group, balancing of the charge of the alkylcarbonate anion and leading to the metalation. The base NEt3 acts as the proton-transfer bridge to promote the transfer of the proton. In addition, the selectivity of the five-membered cyclic carbonates has been investigated. |
| 语种 | 英语 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| WOS记录号 | WOS:000417441400011 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/45205]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Ma, Jun; Han, Buxing |
| 作者单位 | 1.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, CAS Key Lab Colloid Interface & Chem Thermodynam, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Sch Chem & Chem Engn, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Ma, Jun,Lu, Lu,Mei, Qingqing,et al. ZnI2/NEt3-Catalyzed Cycloaddition of CO2 with Propargylic Alcohols: Computational Study on Mechanism[J]. CHEMCATCHEM,2017,9(21):4090-4097. |
| APA | Ma, Jun,Lu, Lu,Mei, Qingqing,Zhu, Qinggong,Hu, Jiayin,&Han, Buxing.(2017).ZnI2/NEt3-Catalyzed Cycloaddition of CO2 with Propargylic Alcohols: Computational Study on Mechanism.CHEMCATCHEM,9(21),4090-4097. |
| MLA | Ma, Jun,et al."ZnI2/NEt3-Catalyzed Cycloaddition of CO2 with Propargylic Alcohols: Computational Study on Mechanism".CHEMCATCHEM 9.21(2017):4090-4097. |
入库方式： OAI收割
来源：化学研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。