Comparative effects of conjugated and deconjugated isomeric enones on the transannular Diels-Alder reaction

被引：5

作者：

Caussanel, F

Deslongchamps, P

Dory, YL

机构：

[1] Univ Sherbrooke, Organ Synth Lab, Sherbrooke, PQ J1H 5N4, Canada

[2] Univ Sherbrooke, Lab Synthese Supramol, Dept Chim, Inst Pharmacol, Sherbrooke, PQ J1H 5N4, Canada

来源：

ORGANIC LETTERS | 2003年 / 5卷 / 25期

关键词：

D O I：

10.1021/ol035791z

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] Two isomeric cyclic trienones 2 and 3 (with four methyl esters at positions 3 and 10) underwent transannular Diels-Alder (TADA) reaction at very different temperatures. This drastic difference could be traced to the capacity of the enone dienophile to be conjugated or unconjugated at the transition state. Molecular modeling could confirm this explanation. The calculated enone proved to be very distorted in transition state ts2, and the TADA reaction temperature was accordingly much higher than the one corresponding to ts3 in which the enone was flat.

引用

页码：4799 / 4802

页数：4

共 25 条

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