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DOI: 10.1039/A702633A (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 2313-2318

Ozonolysis of cholesterol and other Δ5-steroids in the presence of alcohols: a revised mechanism and hydroperoxide structure of the solvent-participated product, confirmed by X-ray analysis

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Zdzisław Paryzek and Urszula Rychlewska

Abstract

The structure of the product formed in the course of the reaction of cholesterol acetate and other Δ5-steroids with ozone in alcohol-containing solvents has been revised. The solvent-participated products are hydroperoxides, 5α-hydroperoxy-7α-alkoxy-5α-B-homo-6-oxasteroids 3 and not the previously claimed cyclic hemiperacetals, 5α-hydroxy-7a-alkoxy-B-dihomo-6,7-dioxacholestane derivatives 1. The final evidence has been obtained from X-ray crystal structure analysis of the selected hydroperoxides 3a, 3c and 3j. It is proposed that hydrogen bonding involving the hydroperoxy and the alkoxy group is responsible for the stability of these hydroperoxides and also exerts a directive effect in the nucleophilic attack on the Criegee intermediate 12 by the alcohol.

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