Isotope effects and the distinction between synchronous, asynchronous, and stepwise Diels-Alder reactions

被引：85

作者：

Singleton, DA ^{[1
]}

Schulmeier, BE ^{[1
]}

Hang, C ^{[1
]}

Thomas, AA ^{[1
]}

Leung, SW ^{[1
]}

Merrigan, SR ^{[1
]}

机构：

[1] Texas A&M Univ, Dept Chem, College Stn, TX 77842 USA

来源：

TETRAHEDRON | 2001年 / 57卷 / 24期

基金：

美国国家卫生研究院;

关键词：

Diels-Alder reaction; isotope effect; asynchronous transition state;

D O I：

10.1016/S0040-4020(01)00354-4

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A. variety of symmetrical or nearly symmetrical Diels-Alder reactions are studied by a combination of experimental isotope effects, theoretical calculations, and rate observations. Becke3LYP calculations predicted highly asynchronous transition structures for Diels-Alder reactions of bis(boryl)acetylenes, dialkyl acetylenedicarboxylates, triazolinediones, and dialkyl maleates. Rate observations and kinetic isotope effects are consistent with these predictions, though the experimental support for the calculated structures is notably ambiguous in some cases. A concerted mechanism is supported for the retro-Diels-Alder reaction of norbornene. Overall, Diels-Alder reactions appear to be only very weakly biased toward synchronous transition states. (C) 2001 Elsevier Science Ltd. All rights reserved.

引用

页码：5149 / 5160

页数：12

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