An electron localization function analysis of the molecular mechanism and the C–O bond formation in the [3+2] cycloaddition reaction involving zwitterionic type between a nitrone and an electron deficient ethyne

IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL
Abdelilah Benallou, Habib El Alaoui El Abdallaoui, H. Garmes
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引用次数: 0

Abstract

The mechanistic nature of a [3+2] cycloaddition reaction involving zwitterionic species has been investigated, and the changes of electron density related to the O–C and C–C bond formation along the intrinsic reaction coordinate have been characterized. This polar [3+2] cycloaddition reaction, which takes place through a non-concerted two-stage one-step mechanism, proceeds with a moderate Gibbs free activation energy of 21 kcal mol−1. The reaction begins by the creation of a pseudoradical centre at the central carbon, first on the dimethyl acetylenedicarboxylate, and second on the nitrone framework. This immediately favours the formation of the first O–C single bond by donation of some electron density of the oxygen atom lone pairs, which represents the most attractive centre in this cycloaddition reaction.
[3+2]环加成反应中氮酮和缺电子乙烷的分子机理和C-O键形成的电子定位函数分析
研究了含两性离子的[3+2]环加成反应的机理,表征了O-C和C-C键沿本征反应座标的电子密度变化。该极性[3+2]环加成反应为非协调两阶段一步反应,吉布斯自由活化能为21 kcal mol−1。反应开始于在中心碳上产生一个伪基中心,首先在二甲基乙炔二羧酸酯上,然后在硝基酮框架上。这立即有利于第一个O-C单键的形成,通过给予氧原子孤对的一些电子密度,这代表了环加成反应中最吸引人的中心。
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来源期刊
CiteScore
2.10
自引率
0.00%
发文量
5
审稿时长
2.3 months
期刊介绍: The journal covers the fields of kinetics and mechanisms of chemical processes in the gas phase and solution of both simple and complex systems.
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