3beta-Hydroxy-5alpha,6alpha-epoxyandrostane-17-one → Androstane-3beta,5alpha,17beta-triol

HRID 42082Notes

Reaction equation

HRID 42082 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].[OH:7][C@H:8]1[CH2:25][CH2:24][C@@:23]2([CH3:26])[C@:10]3([O:28][C@H:11]3[CH2:12][C@@H:13]3[C@@H:22]2[CH2:21][CH2:20][C@@:18]2([CH3:19])[C@H:14]3[CH2:15][CH2:16][C:17]2=[O:27])[CH2:9]1>C1COCC1>[CH3:19][C@:18]12[CH2:20][CH2:21][C@H:22]3[C@@H:13]([CH2:12][CH2:11][C@:10]4([OH:28])[C@:23]3([CH3:26])[CH2:24][CH2:25][C@H:8]([OH:7])[CH2:9]4)[C@@H:14]1[CH2:15][CH2:16][C@@H:17]2[OH:27]

Participants

4

Reactant 2

HCID 70751553beta-Hydroxy-5alpha,6alpha-epoxyandrostane-17-oneHCID 21226445Aluminium lithium hydride

Product 1

HCID 14135090Androstane-3beta,5alpha,17beta-triolYield 74%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred suspension of LiAlH4 (0.247 mg) in THF under N2 (10.5 mL), a solution of 3β-hydroxy-5α,6α-epoxyandrostane-17-one (0.64 g) in THF (20 mL) was added dropwise and the mixture was stirred at reflux for 8 h. The suspension was cooled with an ice bath and then quenched by careful addition of H2O (1 mL) and 4N NaOH (0.20 mL). The mixture was filtered through a Celite pad and the filter cake was washed with THF (3×10 mL). The filtrate was dried over Na2SO4, evaporated to dryness and the residue was purified by flash chromatography (SiO2, n-hexane/CH2Cl2/acetone 40/30/30) to give androstane-3β,5α,17β-triol (0.48 g, 74%). 1H-NMR (300 MHz, DMSO-d6, ppm from TMS): δ 4.37 (1H, d), 4.19 (1H, d), 3.78 (1H, m), 3.62 (1H, s), 3.39 (1H, m), 1.87-0.80 (21H, m), 0.86 (3H, s), 0.59 (3H, s).

Workup

  1. temperatureat reflux for 8 h
  2. temperatureThe suspension was cooled with an ice bath
  3. customquenched by careful addition of H2O (1 mL) and 4N NaOH (0.20 mL)
  4. filtrationThe mixture was filtered through a Celite pad
  5. washthe filter cake was washed with THF (3×10 mL)
  6. dry with materialThe filtrate was dried over Na2SO4
  7. customevaporated to dryness
  8. customthe residue was purified by flash chromatography (SiO2, n-hexane/CH2Cl2/acetone 40/30/30)

Sources & evidence

ORD record
ord-aa3587debb534b9981fb9191b6c31d62
Source dataset
uspto-grants-2013_09
Patent number
US08536160B2

Reaction notes

Loading…