Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (4): 825-831.DOI: 10.6023/cjoc201703037 Previous Articles     Next Articles

Articles

金鸡纳碱衍生伯胺催化1-硝基-2-苯基乙烯与2-甲基丙醛不对称Michael加成反应机理的理论研究

姜海洋a, 李强a, 齐庆杰b, 杨晨曦a, 张丹a   

  1. a 辽宁工程技术大学理学院 阜新 123000;
    b 辽宁工程技术大学安全科学与工程学院 阜新 123000
  • 收稿日期:2017-03-22 修回日期:2017-06-14 出版日期:2018-04-24 发布日期:2017-12-15
  • 通讯作者: 姜海洋 E-mail:jianghaiyang999@163.com
  • 基金资助:

    中国博士后科学基金(No.2016M591451)、辽宁省自然科学基金(No.2017054028)、辽宁省教育厅一般项目(No.LJYL044)、辽宁工程技术大学第六批生产技术问题基金(No.20160086T)和辽宁省大学生创新创业训练计划(No.201610147000044)资助项目.

Theoretical Study on the Conjugate Addition of Asymmetric Michael Addition of trans-1-Nitro-2-phenylethylene to 2-Methylpropion-aldehyde Catalyzed by Cinchona Alkaloid Derived Primary Amine

Jiang Haiyanga, Li Qianga, Qi Qingjieb, Yang Chenxia, Zhang Dana   

  1. a College of Science, Liaoning Technological University, Fuxxin 123000;
    b College of Safety Science and Engineering, Liaoning Technological University, Fuxin 123000
  • Received:2017-03-22 Revised:2017-06-14 Online:2018-04-24 Published:2017-12-15
  • Contact: 10.6023/cjoc201703037 E-mail:jianghaiyang999@163.com
  • Supported by:

    Project supported by the China Postdoctoral Science Foundation Project (No. 2016M591451), the Natural Science Foundation of Liaoning Province (No. 2017054028), the Liaoning Education Department General Project (No. LJYL044), the Sixth Agricultural Technology Problems Foundation of Liaoning Technical University (No. 20160086T) and the Undergraduate Innovation and Entrepreneurship Training Program of Liaoning Province (No. 201610147000044).

The theoretical study is presented for the Michael addition reaction between trans-1-nitro-2-phenylethylene and 2-methylpropionaldehyde catalyzed by (9S)-9-amino-6'-methoxy-10,11-dihydrocinchonan (9-epi-DHQDA) and benzoic acid. All structures, including the reactants, intermediates, transition states and products were optimized. Transition states have been confirmed by the corresponding vibration analysis and intrinsic reaction coordinate (IRC). In addition, nature bond orbital (NBO) and atoms in molecules (AIM) theories have been used to analyze orbital interactions and bond natures. Calculations indicate that the benzoic acid might undergo a proton step to the 9-epi-DHQDA to produce the iminium intermediate. Then the iminium serves as a reactive acceptor to participate in the subsequent nucleophilic addition. Next, a proton transfer process from the tertiary amine to nitronate carbon is found to be rate-determining step, and the enantioselectivity of the catalyzed Michael reaction is also controlled by this step. Finally, one water molecule participates in hydrolysis and C=O bond formation, and results in the formation of product and recovery of catalyst.

Key words: cinchona alkaloid derived primary amine, density functional theory, Michael addition, mechanism, enantioselectivity