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Communication

Dirhodium(II) Caprolactamate: An Exceptional Catalyst for Allylic Oxidation

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Arthur J. Catino, Raymond E. Forslund, and Michael P. Doyle*

Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742

J. Am. Chem. Soc., 2004, 126 (42), pp 13622–13623

DOI: 10.1021/ja045330o

Publication Date (Web): October 2, 2004

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, mdoyle3@umd.edu

Abstract

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.

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Published In Issue October 27, 2004
Received August 3, 2004

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Communication

Dirhodium(II) Caprolactamate: An Exceptional Catalyst for Allylic Oxidation

Abstract

Tools

SciFinder Links

History

Recommend & Share

Related Content

A Mild, Catalytic, and Highly Selective Method for the Oxidation of α,β-Enones to 1,4-Enediones

Mild Manganese(III) Acetate Catalyzed Allylic Oxidation: Application to Simple and Complex Alkenes

Electronic and steric control in carbon-hydrogen insertion reactions of diazoacetoacetates catalyzed by dirhodium(II) carboxylates and carboxamides

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