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A Computational Study on the 4‐Dimethylaminopyridine (DMAP)‐Catalyzed Regioselective [2+4] Cyclization of Allenic Ester with Cyclic Ketimine
ChemistrySelect ( IF 1.9 ) Pub Date : 2018-10-10 , DOI: 10.1002/slct.201802267 Qiuli Liu 1 , Shi-Jun Li 1 , Xue Li. 1 , Ling-Bo Qu 1 , Donghui Wei 1
ChemistrySelect ( IF 1.9 ) Pub Date : 2018-10-10 , DOI: 10.1002/slct.201802267 Qiuli Liu 1 , Shi-Jun Li 1 , Xue Li. 1 , Ling-Bo Qu 1 , Donghui Wei 1
Affiliation
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The reaction mechanisms of [2+4] cyclization of allenic ester and cyclic ketimine catalyzed by 4‐dimethylaminopyridine (DMAP) for forming highly functionalized hydropyridine derivatives were studied theoretically using density functional theory (DFT). Three possible reaction channels, including DMAP‐catalyzed [β,γ]–/[α,β]–[2+4] cyclization channel (i. e., channel A/B) and direct [β,γ]–[2+4] cyclization channel (i. e., channel C) were considered. According to the calculated results, channel A was concluded to be the most energetically favorable among the three channels, and the corresponding product is the main product, which is consistent with the experimental observation. The channel A consists of four steps, i. e., nucleophilic addition on the Cβ atom of allenic ester by DMAP, the stepwise [β,γ]–[2+4] cyclization with ketimine, and the dissociation of DMAP with product. The analyses of global reactivity index (GRI) and frontier molecular orbital (FMO) suggested that DMAP not only enhances the nucleophilicity of allenic ester but also narrows the energy gap of the FMOs involved in the [2+4] cyclization, and thus makes the reaction more easily to occur. Moreover, the non‐covalent interaction (NCI) analysis explored the origin of regioselectivity of the reaction.
中文翻译：
对4-二甲基氨基吡啶（DMAP）催化的环酮亚胺对烯丙基酯的区域选择性[2 + 4]环化的计算研究
利用密度泛函理论（DFT），从理论上研究了4-二甲氨基吡啶（DMAP）催化烯丙酸酯和环状酮亚胺[2 + 4]环化形成高度官能化氢吡啶衍生物的反应机理。三种可能的反应通道，包括DMAP催化的[β，γ] – / [α，β] – [2 + 4]环化通道（即通道A / B）和直接[β，γ] – [2 + 4]考虑了环化通道（即通道C）。根据计算结果，得出通道A在三个通道中是最有利的，而相应的产品是主要产品，这与实验观察一致。通道A包含四个步骤，即 ê，亲核加成在C βDMAP提取烯丙酸酯的原子，逐步地[β，γ] – [2 + 4]与酮亚胺环化，以及DMAP与产物解离。对全球反应指数（GRI）和前沿分子轨道（FMO）的分析表明，DMAP不仅增强了烯丙酸酯的亲核性，而且缩小了[2 + 4]环化中涉及的FMO的能隙，从而使反应更容易发生。此外，非共价相互作用（NCI）分析探索了反应区域选择性的起源。
更新日期：2018-10-10
中文翻译：
对4-二甲基氨基吡啶（DMAP）催化的环酮亚胺对烯丙基酯的区域选择性[2 + 4]环化的计算研究
利用密度泛函理论（DFT），从理论上研究了4-二甲氨基吡啶（DMAP）催化烯丙酸酯和环状酮亚胺[2 + 4]环化形成高度官能化氢吡啶衍生物的反应机理。三种可能的反应通道，包括DMAP催化的[β，γ] – / [α，β] – [2 + 4]环化通道（即通道A / B）和直接[β，γ] – [2 + 4]考虑了环化通道（即通道C）。根据计算结果，得出通道A在三个通道中是最有利的，而相应的产品是主要产品，这与实验观察一致。通道A包含四个步骤，即 ê，亲核加成在C βDMAP提取烯丙酸酯的原子，逐步地[β，γ] – [2 + 4]与酮亚胺环化，以及DMAP与产物解离。对全球反应指数（GRI）和前沿分子轨道（FMO）的分析表明，DMAP不仅增强了烯丙酸酯的亲核性，而且缩小了[2 + 4]环化中涉及的FMO的能隙，从而使反应更容易发生。此外，非共价相互作用（NCI）分析探索了反应区域选择性的起源。
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