Theoretical analysis of mechanism and regio- and stereoselectivity of 1, 3-dipolar cycloaddition of cyclic nitrone and substituted alkenes by DFT method

IF 2.1 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Structural Chemistry Pub Date : 2024-02-14 DOI:10.1007/s11224-024-02292-7

Samir Bouacha

引用次数: 0

Abstract

This study presents a theoretical investigation of the [3 + 2] cycloaddition (32CA) reaction between cyclic nitrone a1 and substituted alkene b1. The mechanism, regioselectivity, and stereoselectivity of this 32CA reaction were analyzed using transition state theory and reactivity indices obtained from conceptual density functional theory (DFT) at the B3LYP/6-311G(d) level of theory. The results indicate that this cycloaddition reaction proceeds via an asynchronous one-step mechanism, exhibiting a non-polar nature and significant activation energies. These theoretical results are in agreement with the experimental observations. The study also employs topological analyses such as ESP, RDG-NCI, and ELF to determine active sites; distinguish hydrogen bonds, van der Waals interactions, and steric repulsive interactions; and predict electron localization, respectively.

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用 DFT 方法对环腈酮与取代烯的 1，3-二极环加成的机理及区域和立体选择性进行理论分析

本研究对环腈酮 a1 和取代烯 b1 之间的 [3 + 2] 环加成（32CA）反应进行了理论研究。利用过渡态理论和在 B3LYP/6-311G(d) 理论水平上从概念密度泛函理论（DFT）获得的反应性指数，分析了该 32CA 反应的机理、区域选择性和立体选择性。结果表明，该环加成反应通过异步一步机理进行，表现出非极性和显著的活化能。这些理论结果与实验观察结果一致。研究还采用了拓扑分析方法，如 ESP、RDG-NCI 和 ELF，分别确定活性位点；区分氢键、范德华相互作用和立体排斥相互作用；以及预测电子定位。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Structural Chemistry 化学-化学综合

CiteScore

3.80

自引率

11.80%

发文量

227

审稿时长

3.7 months

期刊介绍： Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry. We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.