Isopropanol → 5alpha-Hydroxyandrostane-3,6,17-trione

HRID 42102Notes

Reaction equation

HRID 42102 reaction equation
[OH:1][C@H:2]1[CH2:19][CH2:18][C@@:17]2([CH3:20])[C@:4]3([O:22][C@H:5]3[CH2:6][C@@H:7]3[C@@H:16]2[CH2:15][CH2:14][C@@:12]2([CH3:13])[C@H:8]3[CH2:9][CH2:10][C:11]2=[O:21])[CH2:3]1.[OH:23][C@H]1CC[C@@]2(C)[C@@]3(O[C@@H]3C[C@@H]3[C@@H]2CC[C@@]2(C)[C@H]3CCC2=O)C1.CC(O)C>CC(C)=O.CC(C)=O.OS(O)(=O)=O.O=[Cr](=O)=O>[OH:22][C@:4]12[CH2:3][C:2](=[O:1])[CH2:19][CH2:18][C@:17]1([CH3:20])[C@@H:16]1[C@H:7]([C@H:8]3[C@@:12]([CH2:14][CH2:15]1)([CH3:13])[C:11](=[O:21])[CH2:10][CH2:9]3)[CH2:6][C:5]2=[O:23]

Participants

6

Reactant 3

HCID 3776IsopropanolHCID 165865(3beta,5beta,6beta)-5,6-Epoxy-3-hydroxyandrostan-17-oneHCID 70751553beta-Hydroxy-5alpha,6alpha-epoxyandrostane-17-one

Product 1

HCID 250587555alpha-Hydroxyandrostane-3,6,17-trioneYield 75%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 131709961Jones' reagentSolvent

Procedure

To a solution of a 1/1 mixture of 3β-hydroxy-5α,6α-epoxyandrostane-17-one and 3β-hydroxy-5β,6β-epoxyandrostan-17-one (2.10 g, 6.90 mmol) in acetone (38 mL), Jones reagent (8.35 mL) was added dropwise, maintaining the temperature below 40° C. 5 min after completion of the addition, i-PrOH (10 mL) was added and, after further 10 min, the suspension was filtered and the filtrate evaporated to dryness. The residue was treated with H2O (300 mL) and extracted with EtOAc (3×100 mL). The combined organic extracts were washed with H2O (100 mL), 5% aqueous NaHCO3 solution (100 mL), H2O (100 mL), dried over Na2SO4 and evaporated to dryness to give 5α-hydroxyandrostane-3,6,17-trione as a white solid (1.65 g, 75%). 1H-NMR (300 MHz, acetone-d6, ppm from TMS): δ 5.00 (1H, s), 2.85 (2H, m), 2.45-1.25 (17H, m), 1.06 (3H, s), 0.88 (3H, s).

Workup

  1. additionwas added dropwise
  2. temperaturemaintaining the temperature below 40° C
  3. additionwas added and, after further 10 min
  4. filtrationthe suspension was filtered
  5. customthe filtrate evaporated to dryness
  6. additionThe residue was treated with H2O (300 mL)
  7. extractionextracted with EtOAc (3×100 mL)
  8. washThe combined organic extracts were washed with H2O (100 mL), 5% aqueous NaHCO3 solution (100 mL), H2O (100 mL)
  9. dry with materialdried over Na2SO4
  10. customevaporated to dryness

Sources & evidence

ORD record
ord-3ef512b34d404735b95553f78d84d04d
Source dataset
uspto-grants-2013_09
Patent number
US08536160B2

Reaction notes

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