Applied Catalysis A: General 247 (2003) 75–81 Oxidation of saturated and unsaturated alcohols promoted by aluminum alkyls and t-butyl hydroperoxide Antonio Proto a,∗ , Carmine Capacchione a , Arrigo Scettri a , Oriana Motta b a Department of Chemistry, University of Salerno, via S. Allende, 84081 Baronissi (SA), Italy b Department of Educational Science, University of Salerno, via Ponte don Melillo, 84084 Fisciano, Italy Received 15 November 2002; received in revised form 13 January 2003; accepted 13 January 2003 Abstract Saturated and unsaturated alcohols are efficiently converted into the corresponding ketones and epoxy-alcohols by treatment with organic aluminium compounds/t-butyl hydroperoxide systems. In this paper, we have exploited the possibility of using some commercial aluminium alkyls as catalysts for oxidation reactions. Then, since we observed that the increase of alkyls hindrance on aluminium enhances the conversion toward oxidated products, we found of interest to synthesize a more hindered aluminium based compound. The catalytic performance of this latter compound toward oxidation reactions of allylic alcohols was tested and it was found that it is the most attractive both in terms of yield and time of reaction. © 2003 Elsevier Science B.V. All rights reserved. Keywords: Aluminum; Oxidations; Epoxidations; Hydrides; Diastereoselectivity 1. Introduction The conversion of allylic alcohols into epoxy-alcohol and carbonyl compounds represents an important step for preparative processes which lead to more complex molecules. The procedures used to carry out these kind of reactions (oxidations) are usually based on the uses of transition metal reagents in high oxidation states, some of them being toxic. With the aim to avoid the use of these environmentally toxic materi- als researchers have been looking for new procedures suitable for the oxidation of organic functionalities. Insoluble aluminium based compounds such as zeo- lites [1,2] and K-10 Montmorillonite [3], have been found to be cheap and efficient catalysts for the con- ∗ Corresponding author. Tel.: +39-089965234; fax: +39-089965296.a E-mail address: aproto@unisa.it (A. Proto). version of ,-unsaturated and saturated alcohols into epoxy-alcohol and carbonyl compounds. In 1980 Takai et al. [4] used, for the first time, AlMe 3 /t-butyl hydroperoxide (TBHP) as a soluble catalytic system which has good activity and stereo-selectivity (erythro allylic alcohols are preferentially converted in threo epoxy-alcohols). Some of us, in 1999, showed that methyl aluminoxane (MAO)/TBHP soluble catalytic system [5] promotes the epoxidation and oxidation of the allylic alcohols into the corresponding epoxy and carbonyl compounds. This is caused by the presence of a great number of active catalytic aluminium sites in the oligomeric specie. In this work, we present the catalytic perfor- mance toward saturated and unsaturated alcohols of some commercial alkyl aluminium compounds with TBHP in hydrocarbon solvents and under mild pro- cedure oxidation. The possibility to carry out these reactions in mild conditions can be very helpful 0926-860X/03/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0926-860X(03)00081-4