| PPh3催化Mannich反应机理的密度泛函研究 |
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| 引用本文： | 王万辉,杨亚静,李阳,包明.PPh3催化Mannich反应机理的密度泛函研究[J].分子科学学报,2020(2):153-159,I0005. |
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| 作者姓名： | 王万辉 杨亚静 李阳 包明 |
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| 作者单位： | 大连理工大学精细化工国家重点实验室;大连理工大学石油与化学工程学院 |
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| 基金项目： | 辽宁省自然科学基金资助项目(20170540170);中央高校基本科研业务费专项资金资助项目(DUT18LK14)。 |
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| 摘 要： | 通过密度泛函理论研究了PPh3催化苯胺、苯甲醛和乙酰乙酸乙酯三组分Mannich反应的机理.计算结果表明该机理主要分3个步骤进行:PPh3催化乙酰乙酸乙酯发生酮式-烯醇式互变异构得到烯醇;烯醇辅助苯胺和苯甲醛缩合并脱水生成亚胺;亚胺和烯醇通过加成反应生成β-氨基羰基化合物.通过详细的机理研究,发现烯醇从亚胺的背面进攻其亲电C原子的过渡态的相对能量更低,容易得到反式的产物,对实验观察到的非对映选择性进行了合理的解释.
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| 关 键 词： | DFT研究 反应机理 MANNICH反应 非对映选择性 |
A DFT mechanistic study on the PPh3-catalyzed Mannich reaction |
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| WANG Wan-hui,YANG Ya-jing,LI Yang,BAO Ming.A DFT mechanistic study on the PPh3-catalyzed Mannich reaction[J].Journal of Molecular Science,2020(2):153-159,I0005. |
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| Authors: | WANG Wan-hui YANG Ya-jing LI Yang BAO Ming |
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| Institution: | (State Key Laboratory of Fine Chemicels,Dalian University of Technology,Dalian 116023,China;School of Petroleum and Chemical Engineering,Dalian University of Technology,Panjin 124221,China) |
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| Abstract: | Density functional theory calculations were carried out to study the mechanisms of PPh3-catalyzed three-component Mannich reaction of aniline,benzaldehyde,and ethyl acetoacetate.Our calculation results supported that the reaction proceeds in three distinct steps:PPh3-catalyzed keto-enol tautomerism of ethyl acetoacetate to give enol,enol-assisted condensation of aniline and benzaldehyde followed by dehydration to give imine,and the nucleophilic enol attack on the electrophilic carbon of imine to finally give theβ-amino carbonyl products.The detailed mechanistic study also sugguested that the transition state of the enol re-face attack on the electrophilic carbon of imine showed a lower energy barrier and consequently anti-product was formed preferably.This calculation rationalized the observed diastereoselectivity in experiments. |
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| Keywords: | DFT study reaction mechanism Mannich reaction diastereoselectivity |
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