17921-62-9Relevant articles and documents
Synthesis of hydroxylated steroid hormones via conjugate addition of a silyl-cuprate reagent
Garside, Diana,Kirk, David N.,Waldron, Norman M.
, p. 702 - 711 (2007/10/02)
The synthesis of several hydroxylated steroids via conjugate addition of Fleming's silyl-cuprate reagent, (PhMe2Si)2CuLi, a masked hydroxyl group, to the appropriate enone was studied.By this means 7α-hydroxytestosterone (7) was obtained in good yield from 17β-hydroxyandrosta-4,6-dien-3-one (1a), though similar reactions on 17β-hydroxyandrosta-1,4-dien-3-one (8) gave a low yield of 1α-hydroxytestosterone (13) chiefly through the poor conversion of the phenylsilyl intermediate into the halogenosilane. 3β,16α-Dihydroxy-5α-pregnan-20-one (18b) was obtained in a similar manner from 3β-hydroxy- 5α-pregn-16-en-20-one and 5α-cholestane-1α,3α-diol (17) was produced from the 1-en-3-one (14) via conjugate addition of the silyl group, reduction of the carbonyl function, and oxidative removal of the silyl group. - Keywords: hydroxylated steroids; 7α-hydroxytestosterone; 1α-hydroxytestosterone; 3β,16α-dihydroxy-5α-pregnan-20-one; 5α-cholestane-1α,3α-diol
Synthesis of 15β-Hydroxy-24-oxocholesterol and 15β,29-Dihydroxy-7-oxofucosterol
Liu, Dashan,Stuhmiller, Louise M.,McMorris, Trevor C.
, p. 2161 - 2168 (2007/10/02)
3β-Acetoxyandrost-5-en-17-one has been converted into 15β-hydroxy-24-oxocholesterol.Reaction of (17E)-3-β-(dimethyl-t-butylsilyloxy)-15β,16β-epoxypregna-5,17(20)-diene with the magnesium cyanocuprate derivative of 3-(1,3-dioxolan-2-yl)-4-methylpentyl bromide gave (20R)-3β-(dimethyl-t-butylsilyloxy)-15β-hydroxy-24-oxocholesta-5,16-diene 24-ethylene acetal in 80percent yield, and this was converted into the target compound in high yield by catalytic hydrogenation followed by removal of the protecting groups.Reaction of 3β,15β-diacetoxycholest-5-en-24-one with the anion of diethyl cyanomethylphosphonate and reduction of the resulting nitrile with DIBAL-H, gave 15β,29-dihydroxyfucosterol.This was converted into the 3,29-diacetate 15-formate and oxidized with chromium trioxide-3,5-dimethylpyrazole.Removal of the acetate and formate groups with aqueous potassium carbonate afforded 15β,29-dihydroxy-7-oxofucosterol.