Manganese(III)-mediated oxidative free-radical additions of 1,3-dicarbonyl compounds to homobenzonorbornadiene and benzobarrelene: mechanistic studies

被引：18

作者：

Ali, Mohamed Fadelalla ^{[1
]}

Caliskan, Rasit Ali ^{[1
,2
]}

Sahin, Ertan ^{[3
]}

Balci, Metin ^{[1
]}

机构：

[1] Middle E Tech Univ, Dept Chem, TR-06531 Ankara, Turkey

[2] Suleyman Demirel Univ, Dept Chem, TR-32260 Isparta, Turkey

[3] Ataturk Univ, Dept Chem, TR-25240 Erzurum, Turkey

来源：

TETRAHEDRON | 2009年 / 65卷 / 07期

关键词：

Manganese triacetate; Free radicals; Cycloaddition; Rearrangement; Homobenzonorbornadiene; Benzobarrelene; HIGH-TEMPERATURE BROMINATION; GAMMA-LACTONES; METAL-SALTS; BETA-DIESTERS; ACETIC-ACID; CYCLIZATIONS; ACETATE; BENZONORBORNADIENE; DERIVATIVES; ANNULATION;

D O I：

10.1016/j.tet.2008.12.012

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Homobenzonorbornadiene and benzobarrelene were reacted with dimedone/acetylacetone and Mn(OAc)(3) in the presence of Cu(OAc)(2) in acetic acid. Mainly rearranged products having a [2.2.2]skeleton and the nonrearranged dihydrofuran derivatives were obtained. These observations clearly indicated that the second oxidation takes place before the cyclization reaction. Furthermore, intramolecular tandem oxidations were observed where unusually oxyl radicals attack the double bond to form the products. The mechanism of the formation of the products is discussed. (C) 2008 Elsevier Ltd. All rights reserved.

引用

页码：1430 / 1437

页数：8

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