The origin of the halogen effect on reactivity and reversibility of Diels-Alder cycloadditions involving furan

被引：95

作者：

Pieniazek, SN ^{[1
]}

Houk, KN ^{[1
]}

机构：

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

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2006年 / 45卷 / 09期

关键词：

computer chemistry; cycloaddition; halogenation; oxygen heterocycles; retro reactions;

D O I：

10.1002/anie.200502677

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Origin and generality of the halogen effect in Diels-Alder reactions were explored with high-accuracy CBS-QB3 computations. Halogen substitution increases cycloaddition exergonicities and decreases activation barriers. This effect is attributed to the energetic preference for electronegative halogen substituents to be attached to a more highly alkylated, and therefore more electropositive, carbon framework. (Chemical Equation Presented). © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：1442 / 1445

页数：4

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