Application of the HSAB principle for the quantitative analysis of nucleophilicity/basicity of organic compounds with lone-pair electrons  

作　　者：Zheng Zheng Zhen-Ming Liu 

机构地区：[1]State Key Laboratory of Natural and Biomimetic Drugs, Department of Medicinal Chemistry, School of PharmaceuticalSciences, Peking University Health Science Center, Beijing 100191, China

出　　处：《Journal of Chinese Pharmaceutical Sciences》2011年第2期125-132,共8页中国药学（英文版）

基　　金：Foundation items： National Science ＆ Technology Major Project of China （Grant No. 2009ZX09501-002）, National Natural Science Foundation of China （Grant No. 20802006）.

摘　　要：Based on the density functional theory, we described here a method to investigate the quantitative relationship between nucleophilicity/basicity and HSAB-theory-based properties of compounds with lone-pair electrons. Descriptors including global softness, Fukui function, local softness and local mulliken charge were calculated at SVWN/DN＊ level of DFT with PC Spartan Pro. Nucleophilicity and basicity of 28 selected compounds were classified based on intensity. BP algorithm of artificial neural network （ANN） was employed to study the relationship between the descriptors and nucleophilicity/basicity. Cross-validation was carried out to avoid the over-fitting in training of ANN. A BP network was trained to quantify the relationship between HSAB-theory-based properties and nucleophilicity/basicity of compounds with lone-pair electrons. The results show that the prediction based on the network matches with the experimental results well. The local softness and Fukui function have a better relationship with nucleophilicity and local mulliken charge than with the basicity. The trained BP network could be utilized for predicting the nucleophilicity/basicity of compounds or functional groups with lone-pair electrons.

关 键 词：HSAB theory Nucleophilicity/Basicity Density functional theory Fukui function Artificial neural networks Cross-validation Lone-pair electrons 

分 类 号：R916[医药卫生—药学]