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Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

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Regio and stereoselective oxidations of unsaturated steroidal compounds with H2O2 mediated by CH3ReO3

Francesco P Ballistreri¹, Rosa Chillemi, Sebastiano Sciuto

¹Dipartimento di Scienze Chimiche, University of Catania, Viale A. Doria, I-95125 Catania, Italy.

|March 30, 2006

Abstract:

We have investigated the oxidative behavior of sterols such as cholesteryl acetate (1), 7-dehydrocholesteryl acetate (2), ergosteryl acetate (3), cholecalciferol acetate (Vitamin D(3) acetate) (4) and ergocalciferol acetate (Vitamin D(2) acetate) (5) with the oxidant system methyltrioxorhenium/H(2)O(2)/pyridine in order to check potential parameters controlling the selectivity. The reactions, performed in CH(2)Cl(2)/H(2)O at 25 degrees C, have shown good regio- and stereoselectivity. All oxidation products were isolated by high-performance liquid chromatography (HPLC) and characterized by MS(EI) or FAB, (1)H NMR, (13)C NMR, APT, COSY, HSQC, HMBC, ROESY and NOEDS measurements. Seven new oxygenated compounds were also obtained. Under the experimental conditions adopted in this work, only the diene steroids, i.e. 7-dehydrocholesteryl acetate and ergosteryl acetate, undergo hydrolytic oxirane ring opening, whereas Vitamin D(2) and D(3) acetates, containing the triene system and cholesteryl acetate yield only epoxides. The selectivity seems to be controlled by the nucleophilicity of double bonds and by stereoelectronic and steric effects.

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