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The role of benzoic acid in proline-catalyzed asymmetric michael addition: A density functional theory study

文献类型：期刊论文

作者Shi, Hongwei2; Huang, Xiangui2; Liu, Guixia1,2; Yu, Kunqian1; Xu, Congying2; Li, Weihua2; Zeng, Bubing2,3; Tang, Yun2
刊名INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
出版日期2013-05-05
卷号113期号:9页码:1339-1348
关键词density functional theory Michael addition asymmetric catalysis L-proline benzoic acid derivatives proton transfer
ISSN号0020-7608
DOI10.1002/qua.24297
文献子类Article
英文摘要In asymmetric Michael addition between ketones and nitroolefins catalyzed by L-proline, we observed that it was benzoic acid or its derivatives rather than other proton acid that could accelerate the reaction greatly, and different benzoic acid derivatives brought different yields. To explain the experimental phenomena, a density functional theory study was performed to elucidate the mechanism of proline-catalyzed asymmetric Michael addition with benzoic acid. The results of the theoretical calculation at the level of B3LYP/6-311+G(2df,p)//B3LYP/6-31G(d) demonstrated that benzoic acid played two major roles in the formation of nitroalkane: assisting proton transfer and activating the nitro group. In the stage of enamine formation from imine, the energy profiles of benzoic acid derivatives were also calculated to investigate the reasons why different benzoic acid derivatives caused different yields. The results demonstrated that the pKa value was the major factor for p-substituted benzoic acid derivatives to improve the yields, whereas for m/o-substituted benzoic acid derivatives, both pKa value and electronic and steric effects could significantly increase the yields. The calculated results would be very helpful for understanding the reaction mechanism of Michael addition and provide some insights into the selection of efficient additives for similar experiments. (c) 2012 Wiley Periodicals, Inc.
WOS关键词ORGANOCATALYSTS ; NITROOLEFINS ; KETONES ; NITROSTYRENES ; MOLECULES
资助项目Shanghai Committee of Science and Technology[11DZ2260600] ; State Key Laboratory of Drug Research, Chinese Academy of Sciences[SIMM1203KF-13] ; Key Laboratory of Synthetic Chemistry of Natural Substances, Chinese Academy of Sciences[00000000]
WOS研究方向Chemistry ; Mathematics ; Physics
语种英语
WOS记录号WOS:000316630300012
出版者WILEY
源URL[http://119.78.100.183/handle/2S10ELR8/277622]  
专题药物发现与设计中心
中科院受体结构与功能重点实验室
新药研究国家重点实验室
通讯作者Shi, Hongwei
作者单位1.Chinese Acad Sci, Shanghai Inst Mat Med, State Key Lab Drug Res, Shanghai 201203, Peoples R China;
2.E China Univ Sci & Technol, Shanghai Key Lab New Drug Design, Sch Pharm, Shanghai 200237, Peoples R China;
3.Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Synthet Chem Nat Subst, Shanghai 200032, Peoples R China
推荐引用方式
GB/T 7714		 Shi, Hongwei,Huang, Xiangui,Liu, Guixia,et al. The role of benzoic acid in proline-catalyzed asymmetric michael addition: A density functional theory study[J]. INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY,2013,113(9):1339-1348.
APA Shi, Hongwei.,Huang, Xiangui.,Liu, Guixia.,Yu, Kunqian.,Xu, Congying.,...&Tang, Yun.(2013).The role of benzoic acid in proline-catalyzed asymmetric michael addition: A density functional theory study.INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY,113(9),1339-1348.
MLA Shi, Hongwei,et al."The role of benzoic acid in proline-catalyzed asymmetric michael addition: A density functional theory study".INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 113.9(2013):1339-1348.

入库方式： OAI收割

来源：上海药物研究所

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