Dirhodium(II) Caprolactamate: An Exceptional Catalyst for Allylic Oxidation
- 1 October 2004
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (42), 13622-13623
- https://doi.org/10.1021/ja045330o
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.Keywords
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