Understanding the mechanism of polar Diels-Alder reactions

被引：445

作者：

Domingo, Luis R. ^{[1
]}

Saez, Jose A. ^{[1
]}

机构：

[1] Univ Valencia, Dept Quim Organ, E-46100 Valencia, Spain

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2009年 / 7卷 / 17期

关键词：

DENSITY-FUNCTIONAL THEORY; ELECTRON LOCALIZATION FUNCTION; 4+2 CYCLOADDITION REACTIONS; DIMETHYL ACETYLENEDICARBOXYLATE; QUANTITATIVE CHARACTERIZATION; MOLECULAR-MECHANISMS; CATASTROPHE-THEORY; TRANSITION-STATES; REACTANT POLARITY; DFT;

D O I：

10.1039/b909611f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A good correlation between the activation energy and the polar character of Diels-Alder reactions measured as the charge transfer at the transition state structure has been found. This electronic parameter controls the reaction rate to an even greater extent than other recognized structural features. The proposed polar mechanism, which is characterized by the electrophilic/nucleophilic interactions at the transition state structure, can be easily predicted by analyzing the electrophilicity/nucleophilicity indices defined within the conceptual density functional theory. Due to the significance of the polarity of the reaction, Diels-Alder reactions should be classified as non-polar (N), polar (P), and ionic (I).

引用

页码：3576 / 3583

页数：8

共 65 条

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