Towards assessing the aromaticity of the Diels-Alder transition state

被引：18

作者：

Bachrach, Steven M. ^{[1
]}

White, Paul B. ^{[1
]}

机构：

[1] Trinity Univ, Dept Chem, San Antonio, TX 78212 USA

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2007年 / 819卷 / 1-3期

基金：

美国国家科学基金会;

关键词：

Diels-Alder reaction; transtion state; aromaticity; strain energy;

D O I：

10.1016/j.theochem.2007.05.026

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The symmetry of the Diels-Alder transition state depends on the interplay of orbital interactions, aromaticity, which favors a C(s) structure, and strain, which tends to break symmetry. Twenty Diels-Alder reactions are examined at MP4SDTQ/6-312G(d)//B3LYP/ 6-31G(d). The substituents utilized are alkyl groups in order to minimize the effect of orbital interactions. The underlying assumptions are examined and appropriate caveats discussed. These computations provide, as a first approximation, an estimate of 10 kcal mol(-1) for the aromatic stabilization energy in the Diels-Alder TS. (C) 2007 Elsevier B.V. All rights reserved.

引用

页码：72 / 78

页数：7

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