预测亲核反应位点方法的比较

Comparative study on the methods for predicting the reactive site of nucleophilic reaction

预测分子不同位点发生亲核取代反应的活性具有重要的理论和实际意义.目前已提出了许多基于反应物自身电子结构特点的预测方法.本文将碳基化合物、芳香族化合物和吡啶衍生物这3类分子作为测试体系,对14种预测方法的可靠性进行了详细的比较分析.结果表明,体现局部电子软度的方法能很好地预测反应位点,如简缩双描述符方法,但表现静电效应的预测方法,如原子电荷分析和静电势分析,整体表现很差.对于本文中所用的分子体系来讲,简缩双描述符和Hirshfeld电荷分析方法对分子反应位点预测最准确.

Predicting the reactivity of nucleophilic reaction at different sites has important theoretical and practical significance.There are many prediction methods so far that solely based on the electronic structure of reactants have been proposed.In this paper,detailed comparative analyses on the reliability of 14 methods are carried out and three series of molecules,carbonyl compounds,aromatic hydrocarbons and pyridine derivatives are exploited as test systems.It is found out that the methods reflecting local electronic softness,such as condensed dual descriptor,have satisfactory prediction ability;while the ones reflecting electrostatic effect,such as atomic charge analysis and electrostatic potential analysis,have evidently worse overall performance.For all systems of interest,condensed dual descriptor and Hirshfeld charge display the most robust predictive capacity.