合成路线1

This compound has been obtained by different ways: 1. The fermentation of 3beta-hydroxy-15beta,16beta-methylene-5-androsten-17-one (I) or 3beta-acetoxy-15beta,16beta-methylene-5-androsten-17-one (II) with Botryodiplodia malorum gives the corresponding 3beta,7beta-dihydroxy derivative (III), which is regioselectively silylated with Tbdms-Cl and imidazole to yield the 3-beta-silylated compound (IV). The epoxidation of (IV) by means of tert-butyl hydroperoxide catalyzed by VO(acetonylacetonate)2 complex affords the corresponding epoxide (V), which is treated with PPh3 and CCl4 in dichloromethane to provide the 7-alpha-chloro derivative (VI). The desilylation of (VI) with HCl in THF/methanol gives the 3beta-hydroxy compound (VII), which is treated with Zn in AcOH/THF to yield 3beta, 5beta-dihydroxy-15beta,16beta-methylene-6-androsten-17-one (VIII) (1). The cyclopropanation of (VIII) with diiodomethane and Zn in hot ethyleneglycol dimethylether gives 3beta,5beta-dihydroxy-6beta,7beta:15beta,16beta-bismethyleneandrostan-17-one (IX), which is condensed with propargyl alcohol (X) by means of K-OEt in THF, yielding 17alpha-(3-hydroxy-1-propynyl)-6beta,7beta:15beta,16beta-bismethyleneandrostan-3,5beta,17beta-triol (XI). The hydrogenation of (XI) with H2 over Pd/C in THF/methanol/pyridine affords the corresponding 17alpha-(3-hydroxypropyl) derivative (XII), which is finally oxidized, lactonized and dehydrated by means of CrO3 in hot pyridine/water. 2. Alternatively, the 17alpha-(3-hydroxypropyl) derivative (XII) can be oxidized with RuCl3 and NaBrO3 in hot acetonitrile/water, giving the hydroxy carbolactone (XIII), which is finally dehydrated by means of Ts-OH in THF. 3. Similar synthetic pathways have been described replacing the Tbdms protecting group with either dimethyl(3-methylbutyl)silyl or tribenzylsilyl groups.