Dirhodium(II) caprolactamate: An exceptional catalyst for allylic oxidation

被引：213

作者：

Catino, AJ ^{[1
]}

Forslund, RE ^{[1
]}

Doyle, MP ^{[1
]}

机构：

[1] Univ Maryland, Dept Chem & Biochem, College Pk, MD 20742 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 42期

关键词：

D O I：

10.1021/ja045330o

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The oxidation of organic molecules represents a fundamentally important chemical process. Particularly important is allylic oxidation, whereby a single methylene unit is converted directly into a carbonyl group. In this communication, we report that dirhodium(II) caprolactamate [Rh2(cap)4] in combination with tert-butyl hydroperoxide (terminal oxidant) effectively catalyzes the allylic oxidation of a variety of olefins and enones. The reaction is completely selective, tolerant of air/moisture, and can be performed with as little as 0.1 mol % catalyst in minutes. A mechanistic proposal involving redox chain catalysis has been put forth, as well as evidence for the intermediacy of a higher valent dirhodium tert-butyl peroxy complex. Copyright © 2004 American Chemical Society.

引用

页码：13622 / 13623

页数：2

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