The effect of solvent on a lewis acid catalyzed Diels-Alder reaction, using computed and experimental kinetic isotope effects

被引：20

作者：

Acevedo, O

Evanseck, JD

机构：

[1] Duquesne Univ, Ctr Computat Chem, Pittsburgh, PA 15282 USA

[2] Duquesne Univ, Dept Chem & Biochem, Pittsburgh, PA 15282 USA

来源：

ORGANIC LETTERS | 2003年 / 5卷 / 05期

关键词：

D O I：

10.1021/ol027408g

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] A new transition structure for the Diels-Alder reaction between isoprene and acrolein catalyzed by Et2AlCl is found to reconcile reported discrepancies between computed and observed secondary kinetic isotope effects (KIEs). Including the effect of solvent realigns the computed results with experiment demonstrating the importance of nonbond interactions at transition structures. Comparison of experimental and newly predicted KIE data reaffirms the ability of theory and experiment to probe the mechanism and transition structure geometry of organic reactions.

引用

页码：649 / 652

页数：4

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