Reactions of hydroperoxides with iron(III) porphyrins: Heterolytic cleavage followed by hydroperoxide oxidation

被引：49

作者：

Traylor, TG ^{[1
]}

Kim, C ^{[1
]}

Fann, WP ^{[1
]}

Perrin, CL ^{[1
]}

机构：

[1] Univ Calif San Diego, Dept Biochem & Chem, La Jolla, CA 92093 USA

来源：

TETRAHEDRON | 1998年 / 54卷 / 28期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

D O I：

10.1016/S0040-4020(98)00444-X

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Reaction of alpha,alpha-dimethylphenethyl hydroperoxide with iron(III) tetramesitylporphyrin in protic solvent gives alkoxy-radical products and little epoxide. Such observations are usually interpreted as evidence for homolysis of the O-O bond in the catalytic process. Yet the same products are now obtained under similar conditions from the reaction of this hydroperoxide with the high-valent oxene (Fe+=0), generated unambiguously. Therefore such products are not necessarily evidence for homolysis but are consistent with heterolysis. Nevertheless, the solvent can affect the nature of O-O cleavage. (C) 1998 Elsevier Science Ltd. All rights reserved.

引用

页码：7977 / 7986

页数：10

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