Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/69620
Type: Artigo de periódico
Title: Homogeneously catalyzed epoxidation of alpha,beta-unsaturated ketones using simple aluminum salts and aqueous H2O2-Is it possible?
Author: Rinaldi, R
de Oliveira, HFN
Schumann, H
Schuchardt, U
Abstract: Simple aluminum salts activate hydrogen peroxide towards alpha,beta-unsaturated ketones, affording as major products alpha,beta-epoxyketones. The pathway of this reaction involves the interaction between [Al(H2O)(6)](3+) and H2O2, through hydrogen bonds, in the second-coordination sphere. This interaction enhances the proton exchange between non-coordinated water and hydrogen peroxide. as detected by H-1 NMR experiments. By this means, the hydroperoxide anion, formed as reactive intermediate in the proton exchange between H2O and H2O2, can be trapped by alpha,beta-unsaturated ketones. Surprisingly, this pathway is not followed when diethylmaleate is used as substrate. In this case, the radical addition of THF to the C=C bond of diethylmaleate takes place with high selectivity, affording 2-(THF)-derivatives with high yields. (C) 2009 Elsevier B.V. All rights reserved.
Subject: O-O activation
Oxidation
Aluminum
Peroxide
Second-coordination sphere
Enones
Radical reactions
Country: Holanda
Editor: Elsevier Science Bv
Rights: fechado
Identifier DOI: 10.1016/j.molcata.2009.04.005
Date Issue: 2009
Appears in Collections:Artigos e Materiais de Revistas Científicas - Unicamp

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