Meisenheimer complexes as hidden intermediates in the aza-SNAr mechanism.,Organic & Biomolecular Chemistry

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Meisenheimer complexes as hidden intermediates in the aza-SNAr mechanism.
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2020-05-18 , DOI: 10.1039/d0ob00600a
Rodrigo Ormazábal-Toledo ₁ , Sebastián Richter ₂ , Andrés Robles-Navarro ₃ , Boris Maulén ₄ , Ricardo A Matute ₅ , Sebastián Gallardo-Fuentes ₂

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In this work we report a computational study about the aza-S_NAr mechanism in fluorine- and chlorine-containing azines with the aim to unravel the physical factors that determine the reactivity patterns in these heterocycles towards propylamine. The nature of the reaction intermediate was analyzed in terms of its electronic structure based on a topological analysis framework in some non-stationary points along the reaction coordinate. The mechanistic dichotomy of a concerted or a stepwise pathway is interpreted in terms of the qualitative Diabatic Model of Intermediate Stabilization (DMIS) approach, providing a general mechanistic picture for the S_NAr process involving both activated benzenes and nitrogen-containing heterocycles. With the information collected, a unified vision of the Meisenheimer complexes as transition state, hidden intermediate or real intermediate was proposed.

中文翻译：

Meisenheimer配合物是aza-SNAr机制中的隐藏中间体。

在这项工作中，我们报告了有关含氟和氯的嗪中aza-S _N Ar机理的计算研究，目的是弄清确定这些杂环对丙胺的反应方式的物理因素。在沿着反应坐标的一些非平稳点上，基于拓扑分析框架，根据其电子结构分析了反应中间体的性质。协调或逐步的途径的机械二分法是根据定性的中间稳定绝热模型（DMIS）方法来解释的，为S _N提供了一般的力学图景。Ar过程涉及活化的苯和含氮杂环。利用收集到的信息，提出了迈森海默复合物的统一愿景，即过渡态，隐藏的中间体或真实的中间体。

更新日期：2020-05-18

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