A theoretical study of intramolecular Diels-Alder reactions, diene-(CH2)n-dienophile (n=1, 2, 3 and 4)

被引：11

作者：

Vijaya, R ^{[1
]}

Sastry, GN ^{[1
]}

机构：

[1] Pondicherry Univ, Dept Chem, Pondicherry 605014, India

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2002年 / 618卷 / 03期

关键词：

Diels-Alder reaction; concerted mechanism; stepwise mechanism; theoretical studies; semiempirical; density functional theory;

D O I：

10.1016/S0166-1280(02)00405-0

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：

Quantum chemical calculations at the hybrid density functional, B3LYP/6-31G* and the semiempirical PM3 levels were performed on model intramolecular systems where the diene and dienophile are linked by the hydrocarbon spacer, -(CH2)(n)-. Six of the possible reaction pathways; namely one concerted and two stepwise each for the cis- and trans-cycloadditions are considered. All the stationary points on the potential energy surface were identified and characterized by frequency calculations at PM3 level. The study establishes that the concerted mechanism prevails over the stepwise even in the presence of the structural constrains imposed by varying intervening spacer chain lengths. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：201 / 208

页数：8

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