Pericyclic reactions of cyclopentadienones with nonactivated olefins in phenolic solvents. Enhancement of the reactivity and periselectivity

被引：15

作者：

Jikyo, T ^{[1
]}

Eto, M ^{[1
]}

Harano, K ^{[1
]}

机构：

[1] Kumamoto Univ, Fac Pharmaceut Sci, Kumamoto 862, Japan

来源：

TETRAHEDRON | 1999年 / 55卷 / 19期

关键词：

D O I：

10.1016/S0040-4020(99)00259-8

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The solvent effect of phenols on the reactivity and periselectivity for the pericyclic reactions of cyclopentadienones with olefins involving conjugated medium-ring polyenes has been investigated. The use of phenols as a solvent accelerates the reaction rates of cycloadditions of cyclopentadienones with nonactivated olefins. In the reaction of cycloheptatriene in p-chlorophenol, the exo [4+6]pi cycloadduct was produced predominantly, in which a 15-fold increase of the reaction rate was observed as compared with that in benzene. The [3,3]-sigmatropy and decarbonylation of the primary cycloadducts were also accelerated by phenols. The possible role of phenols is discussed on the basis of kinetic and molecular orbital (MO) calculation data. (C) 1999 Elsevier Science Ltd. All rights reserved.

引用

页码：6051 / 6066

页数：16

共 25 条

[1] DIMERIZATION OF CYCLOPENTADIENONES [J].