Synthesis of 16 alpha,19-dihydroxy-4-androstene-3,17-dione and 3 beta,16 alpha,19-trihydroxy-5-androsten-17-one and their 17 beta-hydroxy-16-keto isomers.
3 beta,16 alpha,19-Trihydroxy-5-androsten-17-one and 16 alpha,17-dihydroxy-4-androstene-3,17-dione were synthesized from the 5 alpha-bromo-6 beta,19-epoxy-17-ketone derivative 1, using the bromination at C-16 alpha of the 17-ketone 1 and the controlled alkaline hydrolysis of the 16 alpha-bromo-17-ketones 2 and 11 as key reactions. Zinc dust reductive cleavage of the 6 beta,19-epoxy-16 alpha-hydroxy-17-ketones 4 and 12, produced by controlled hydrolysis, gave the corresponding 19-alcohol derivatives 6 and 14, which were rearranged to the 17 beta-hydroxy-16-ketones 7 and 15 when treated with sodium hydroxide. The 3 beta,16 alpha,17 beta,19-tetrol 8 was obtained from the 16 alpha-ketol 6 by reaction with sodium borohydride.
Numazawa
M
M
Tohoku College of Pharmacy, Sendai, Japan.
Mutsumi
A
A
Ogata
M
M
Osawa
Y
Y
D000735:Androstenedione / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D000737:Androstenols / Q000138:chemical synthesis*; D055598:Chemical Phenomena; D002621:Chemistry; D007536:Isomerism
D000737:Androstenols; C056896:3,16,19-trihydroxy-5-androsten-17-one; D000735:Androstenedione; C056897:16,19-dihydroxy-4-androsten-3,17-dione