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
This publication has 20 references indexed in Scilit:
- Highly Enantioselective Copper−Bisoxazoline-Catalyzed Allylic Oxidation of Cyclic Olefins with tert-Butyl p-nitroperbenzoateJournal of the American Chemical Society, 2002
- Hydroperoxides as pseudohalides: oxidation, oxidative alkylation, acylation and arylation of acrylonitrileJournal of the Chemical Society, Chemical Communications, 1995
- Electronic and steric control in carbon-hydrogen insertion reactions of diazoacetoacetates catalyzed by dirhodium(II) carboxylates and carboxamidesJournal of the American Chemical Society, 1993
- Electrochemical studies of a series of dirhodium(II) complexes with acetate and acetamidate bridging ligandsInorganic Chemistry, 1984
- RHODIUM(II) ACETATE: AN EFFECTIVE HOMOGENEOUS CATALYST FOR SELECTIVE ALLYLIC OXIDATION AND CARBON–CARBON BOND FISSION OF OLEFINSChemistry Letters, 1982
- Substituent and solvent effects on the electrochemical properties of tetra-.mu.-carboxylato-dirhodium(II)Inorganic Chemistry, 1978
- Catalyst-product dependency in the transition metal catalyzed decomposition of ethyl 3-diazo-2-oxopropionate. An unusual Wolff rearrangementThe Journal of Organic Chemistry, 1977
- Di-tert-butyl trioxide and di-tert-butyl tertoxideJournal of the American Chemical Society, 1967
- Oxygen-Rich Intermediates in the Low-Temperature Oxidation of t-Butyl and Cumyl HydroperoxidesJournal of the American Chemical Society, 1966
- THE BASE CATALYZED DECOMPOSITION OF A DIALKYL PEROXIDEJournal of the American Chemical Society, 1951