Collect. Czech. Chem. Commun.
1997, 62, 109-123
https://doi.org/10.1135/cccc19970109
Synthesis of (19E)-3β,7β-Dihydroxy-17-oxoandrost-5-en-19-al 19-(O-Carboxymethyl)oxime, New Hapten for 7β-Hydroxydehydroepiandrosterone (3β,7β-Dihydroxyandrost-5-en-17-one)
Vladimír Pouzar, Tereza Slavíková and Ivan Černý
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,166 10 Prague 6, Czech Republic
Abstract
(19E)-3β,7β-Dihydroxy-17-oxoandrost-5-en-19-al 19-(O-carboxymethyl)oxime (26) was prepared in 15 steps from 17-oxoandrost-5-en-3β-yl benzoate (2, DHEA benzoate). Protection of position 17 by a borohydride reduction and acetylation, subsequent functionalization of position 19 by hypoiodite reaction, oxidation to 19-aldehyde and oximation gave successively (19E)-19-oxoandrost-5-ene-3β,17β-diyl 17-acetate 3-benzoate 19-(O-carboxymethyl)oxime methyl ester (10). Then 7-keto group was introduced by allylic oxidation with chromium(VI) oxide-3,5-dimethylpyrazole complex and stereoselectively reduced by borohydride in the presence of cerium(III) ions into 7β-hydroxy group. After protection as 7-isobutyrate the acetate at position 17 was removed and oxidation recovered 17-ketone. Final deprotection revealed both hydroxyl and carboxyl groups, giving desired 19-CMO 7β-hydroxy DHEA designed as hapten for immunassays.
Keywords: 7β-Hydroxy DHEA; Hapten; Oxime.
