Epoxidation of Diosgenin, 25(R)-1,4,6-Spirostatrien-3-one and 25(R)-4,6-Spirostadien-3β-ol.docVIP

Molecules 2003, 8, 886-893 molecules ISSN 1420-3049 Epoxidation of Diosgenin, 25(R)-1,4,6-Spirostatrien-3-one and 25(R)-4,6-Spirostadien-3β-ol Eunsook Ma* and Jongwon Kim College of Pharmacy, Catholic University of Daegu, Hayang, 712-702, Korea, Tel. 82-053-850-3621, Fax. 82-053-850-3602. * Author to whom correspondence should be addressed; E-mail: masook@cataegu.ac.kr Received: 18 September 2003; in revised form: 12 December 2003 / Accepted: 18 December 2003 / Published: 31 December 2003 Abstract: Upon treatment of 25(R)-spirost-5-en-3β-ol (diosgenin), 25(R)-1,4,6- spirostatrien-3-one and 25(R)-4,6-spirostadien-3β-ol with 30% H O and 5% NaOH in 2 2 methanol, diosgenin did not react, 25(R)-1,4,6-spirostatrien-3-one was converted to 25(R)-1α,2α-epoxy-4,6-spirostadien-3-one 25(R)-4,6-spirostadien-3β-ol and was oxidized to give a small amount of 25(R)-4,6-spirostadien-3-one, while most of the original starting material remained unchanged. On the other hand, reactions of diosgenin, 25(R)-1,4,6-spirostatrien-3-one and 25(R)-4,6-spirostadien-3β-ol with m-chloroperoxy- benzoic acid in chloroform yielded 25(R)-5α,6α-epoxyspirostan-3β-ol, 25(R)-6α,7α- epoxy-1,4-spirostadien-3-one and 25(R)-4β,5β-epoxy-6-spirosten-3β-ol, respectively. Keywords: Diosgenin, Stereoselective epoxidation, H O , m-Chloroperoxybenzoic 2 2 acid  887 Molecules 2003, 8 Introduction Diosgenin (25(R)-spirost-5-en-3β-ol) is the steroidal saponin which is isolated from the Mexican yam (Dioscorea). Estrogenic, progesterogenic and anti-inflammatory effects have been hypothesized for diosgenin due to its structural similarity to estrogen and progesterone precursors [1]. Diosgenin has been reported to lower serum cholesterol in chicken and rabbits fed cholesterol and to decrease liver cholesterol in cholesterol-fed rats, an action associated with increased rates of choleste