Experimental Diels-Alder Reactivities of Cycloalkenones and Cyclic Dienes Explained through Transition-State Distortion Energies

被引：119

作者：

Paton, Robert S. ^{[1
]}

Kim, Seonah ^{[2
]}

Ross, Audrey G. ^{[3
]}

Danishefsky, Samuel J. ^{[3
]}

Houk, K. N. ^{[2
]}

机构：

[1] Univ Oxford, Chem Res Lab, Oxford OX1 3TA, England

[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[3] Columbia Univ, Dept Chem, New York, NY 10027 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 44期

基金：

美国国家科学基金会;

关键词：

cycloaddition; Diels-Alder reaction; polycycles; stereoselectivity; strained molecules; CYCLOADDITIONS; DISTORTION/INTERACTION;

D O I：

10.1002/anie.201103998

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Quantum chemical calculations are used to investigate the experimentally measured reactivities of cyclic dienes and cycloalkenones in the Diels-Alder reaction. The interaction energies (red) are nearly constant; differences arise in changes in distortion energies of both dienophile (blue) and diene (green; see picture, Ea=activation energy; values in kcal mol-1). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：10366 / 10368

页数：3

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