3(R)-Pyrrolidinyloxyamine dihydrochloride → (2R,3E,8R,9S,10S,13S,14S)-2-fluoro-10,13-dimethyl-3-[(3R)-pyrrolidin-3-yl]oxyimino-2,4,5,6,7,8,9,11,12,14,15,16-dodecahydro-1H-cyclopenta[a]phenanthren-17-one;hydrochloride

HRID 1182865Notes

Reaction equation

HRID 1182865 reaction equation
[F:1][C@@H:2]1[CH2:19][C@@:18]2([CH3:20])[CH:5]([CH2:6][CH2:7][C@@H:8]3[C@@H:17]2[CH2:16][CH2:15][C@@:13]2([CH3:14])[C@H:9]3[CH2:10][CH2:11][C:12]2=[O:21])[CH2:4][C:3]1=O.[ClH:23].Cl.[NH:25]1[CH2:29][CH2:28][C@@H:27]([O:30][NH2:31])[CH2:26]1>N1C=CC=CC=1>[ClH:23].[NH:25]1[CH2:29][CH2:28][C@@H:27]([O:30]/[N:31]=[C:3]2\[CH2:4][CH:5]3[C@:18]([CH3:20])([CH2:19][C@H:2]\2[F:1])[C@@H:17]2[C@H:8]([C@H:9]4[C@@:13]([CH2:15][CH2:16]2)([CH3:14])[C:12](=[O:21])[CH2:11][CH2:10]4)[CH2:7][CH2:6]3)[CH2:26]1

Participants

4

Reactant 2

HCID 667139183(R)-Pyrrolidinyloxyamine dihydrochlorideHCID 687323102alpha-Fluoroandrostane-3,17-dione

Product 1

HCID 87574048(2R,3E,8R,9S,10S,13S,14S)-2-fluoro-10,13-dimethyl-3-[(3R)-pyrrolidin-3-yl]oxyimino-2,4,5,6,7,8,9,11,12,14,15,16-dodecahydro-1H-cyclopenta[a]phenanthren-17-one;hydrochlorideYield 91%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

2α-Fluoroandrostane-3,17-dione (315 mg) and 3-(R)-pyrrolidinyloxyamine dihydrochloride (Preparation 12, 190 mg) were dissolved in pyridine (5 ml) and stirred at RT for 1 h. After evaporation of the solvent, the crude reaction mixture was purified by flash chromatography (SiO2, CHCl3/MeOH/26% NH4OH 90/10/1). To the resulting oil obtained after fractions evaporation, dissolved in a 1/1 mixture of EtOAc/Et2O (20 ml) and cooled with an ice bath, an excess of 2N HCl solution in Et2O was added. The title compound I-bh was obtained, after filtration, as a white solid in 91% yield.

Workup

  1. customAfter evaporation of the solvent
  2. customthe crude reaction mixture
  3. customwas purified by flash chromatography (SiO2, CHCl3/MeOH/26% NH4OH 90/10/1)
  4. customTo the resulting oil obtained
  5. customafter fractions evaporation
  6. dissolutiondissolved in a 1/1 mixture of EtOAc/Et2O (20 ml)
  7. temperaturecooled with an ice bath
  8. additionan excess of 2N HCl solution in Et2O was added

Sources & evidence

ORD record
ord-2cf1bb7261684d68972c70297a2257bf
Source dataset
uspto-grants-2014_03
Patent number
US08664210B2

Reaction notes

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