1,4-Addition of vinylmagnesium bromide to .ALPHA.,.BETA.-unsaturated steroidal ketones. II. Reaction of 1-En-3-oxo steroids.

The Metabolism of Anabolic-Androgenic Steroids in The Greyhound

“…Mesterolone contains a 1α-methyl substituent oriented axially on the 5α-androstane steroid framework. As previously described [13], this group blocks the lower face of the 3-ketone such that hydride reduction affords mixtures of the 3α-and 3β-alcohols.…”

“…). The organic layer was dried (MgSO4) and concentrated to give a white solid which was purified by flash column chromatography using 10% ethyl acetate in hexane to give the title COCH3), 1.99 (3H, s, COCH3), 0.931 (3H, s, CH3), 0.926 (3H, s, CH3);13 C NMR (100 MHz, CDCl3) δ 214.1, 170.7, 170.4, 74.0, 72.6, 48.8, 47.8, 41.8, 40.7, 35.3, 35.0, 34.8, 32.2, 31.6, 29.7, 26.7, 26.6, 25.0, 23.3, 21.5, 20.9, 19.8, 14.3; HRMS (+EI) calcd for C23H34O5 (M •+ ) 390.2406, found 390.2408. OD) δ 85.0, 80.7, 72.3, 49.6, 47.5, 43.6, 42.0, 37.7, 37.2, 36.4, 35.8, 34.8, 33.3, 31.1, 28.3, 37.4, 23.9, 21.1, 18.2, 15.0; HRMS (+EI) calcd for C20H34O3 .2.7 19-Nor-5β,17α-pregnane-3α,16α,17β-triol and 19-nor-5β,17β-pregnane-3α,16α,17α-triolThe title compound was synthesized on a small scale from 19-noretiocholanolone by a route analogous to that described above (section 2.2.6), with the exception that the 17β-ethyl substituent was introduced via the 17-ketone through a process of ethynylation with lithium acetylide ethylenediamine complex followed by hydrogenation[17].…”