Collect. Czech. Chem. Commun. 1984, 49, 881-891

Glucosylation of 5-androsten-3β-ol derivatives containing butenolide, furan or unsaturated ester moieties in the side chain

Ivan Černý, Vladimír Pouzar, Pavel Drašar, Miloš Buděšínský and Miroslav Havel

Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6


3-O-(Tetra-O-acetyl-β-D-glucopyranosyl) derivatives II, V, XV and XX were prepared from 5-androstene-3β,17β-diol 17-benzoate (I), (20R)-3β-hydroxy-21-nor-5,22-choladien-(24 -20)-olide (IV), 17β-(2-furyl)-5-androsten-3β-ol (XIV) and methyl (20E)-3β-hydroxy-5,20-pregnadiene-21-carboxylate (XIX), respectively, using tetra-O-acetyl-α-D-glucopyranosyl bromide and silver silicate. The furyl derivative XIV was obtained from methyl 3β-methoxymethyletienate VIII by reaction sequence in which the key reactions were alkylation of the keto sulfoxide IX with bromoacetate, cyclization of the obtained product with sodium borohydride and reduction of the mixture of lactones XI and XII with diisobutylaluminium hydride. The unsaturated ester XIX was prepared from 3β-acetoxy-5-androstene-17β-carbaldehyde (XVII) by treatment with diethyl methoxycarbonylmethylphosphonate and deacetylation of the formed acetyl derivative XVIII. Deacetylation of the acetyl derivatives II, XV and XX afforded the glucosides III,XVI and XXI, respectively; the deacetylation of V was accompanied by opening of the lactone ring under formation of the methyl 21-nor-20-oxo-5-cholen-24-oate derivative VI.