Citation: Jiang Haiyang, Li Qiang, Qi Qingjie, Yang Chenxi, Zhang Dan. 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[J]. Chinese Journal of Organic Chemistry, ;2018, 38(4): 825-831. doi: 10.6023/cjoc201703037 shu

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

a.
College of Science, Liaoning Technological University, Fuxxin 123000
b.
College of Safety Science and Engineering, Liaoning Technological University, Fuxin 123000

Corresponding author: Jiang Haiyang, jianghaiyang999@163.com
Received Date: 22 March 2017
Revised Date: 14 June 2017
Available Online: 15 April 2017
Fund Project: 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 Undergraduate Innovation and Entrepreneurship Training Program of Liaoning Province 201610147000044the Natural Science Foundation of Liaoning Province 2017054028the China Postdoctoral Science Foundation Project 2016M591451the Liaoning Education Department General Project LJYL044the Sixth Agricultural Technology Problems Foundation of Liaoning Technical University 20160086T

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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.
- cinchona alkaloid derived primary amine,
- density functional theory,
- Michael addition,
- mechanism,
- enantioselectivity
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