6-Hydroximino-4-androstene-3,17-dione → (6E,8R,9S,10R,13S,14S)-6-hydroxyimino-10,13-dimethyl-3-[(3S)-pyrrolidin-3-yl]oxyimino-1,2,7,8,9,11,12,14,15,16-decahydrocyclopenta[a]phenanthren-17-one

HRID 42077Notes

Reaction equation

HRID 42077 reaction equation
[OH:1]/[N:2]=[C:3]1\[CH2:4][C@@H:5]2[C@@H:14]([C@:15]3([CH3:22])[C:20]\1=[CH:19][C:18](=O)[CH2:17][CH2:16]3)[CH2:13][CH2:12][C@@:10]1([CH3:11])[C@H:6]2[CH2:7][CH2:8][C:9]1=[O:23].Cl.Cl.[NH:26]1[CH2:30][CH2:29][C@H:28]([O:31][NH2:32])[CH2:27]1>>[NH:26]1[CH2:30][CH2:29][C@H:28]([O:31][N:32]=[C:18]2[CH2:17][CH2:16][C@@:15]3([CH3:22])[C:20](/[C:3](=[N:2]/[OH:1])/[CH2:4][C@@H:5]4[C@@H:14]3[CH2:13][CH2:12][C@@:10]3([CH3:11])[C@H:6]4[CH2:7][CH2:8][C:9]3=[O:23])=[CH:19]2)[CH2:27]1

Participants

3

Reactant 2

HCID 111308686-Hydroximino-4-androstene-3,17-dioneHCID 68728672(S)-3-pyrrolidinyloxyamine dihydrochloride

Product 1

HCID 136404308(6E,8R,9S,10R,13S,14S)-6-hydroxyimino-10,13-dimethyl-3-[(3S)-pyrrolidin-3-yl]oxyimino-1,2,7,8,9,11,12,14,15,16-decahydrocyclopenta[a]phenanthren-17-oneYield 65%

Procedure

The title compound I-dw was obtained following the procedure described in Example 100 and starting from 6-(E)-hydroxyiminoandrost-4-ene-3,17-dione (II-bw, Prepn. 63, 200 mg) and 3-(S)-pyrrolidinyloxyamine dihydrochloride (III-d, Prepn. 4) (110 mg). The crude product (1/1 ratio of the E/Z isomers) was purified by flash chromatography (SiO2, CH2Cl2/MeOH/26% NH4OH 90/10/1). The less polar fractions were evaporated to dryness to give the title compound I-dw in 65% yield. 1H-NMR (300 MHz, DMSO-d6, ppm from TMS): δ 10.72 (1H, bs), 6.16 (1H, bs), 4.69 (1H, m), 3.36-3.10 (7H, m), 2.60-1.10 (16H, m), 0.96 (3H, s), 0.83 (3H, s).

Workup

  1. customThe crude product (1/1 ratio of the E/Z isomers) was purified by flash chromatography (SiO2, CH2Cl2/MeOH/26% NH4OH 90/10/1)
  2. customThe less polar fractions were evaporated to dryness

Sources & evidence

ORD record
ord-44a31d2c1cb54fe18b641b7ac37397c9
Source dataset
uspto-grants-2013_09
Patent number
US08536160B2

Reaction notes

Loading…