Estra-1,3,5(10),16-tetraen-6-one-3-yl acetate → Estra-1,3,5(10),16-tetraen-3,6-diol

HRID 275677Notes

Reaction equation

HRID 275677 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C([O:10][C:11]1[CH:28]=[CH:27][C:26]2[C@@H:25]3[C@H:16]([C@H:17]4[C@@:21]([CH2:23][CH2:24]3)([CH3:22])[CH:20]=[CH:19][CH2:18]4)[CH2:15][C:14](=[O:29])[C:13]=2[CH:12]=1)(=O)C>C1COCC1>[CH3:22][C@:21]12[CH2:23][CH2:24][C@H:25]3[C@@H:16]([CH2:15][CH:14]([OH:29])[C:13]4[CH:12]=[C:11]([OH:10])[CH:28]=[CH:27][C:26]=43)[C@@H:17]1[CH2:18][CH:19]=[CH:20]2

Participants

4

Reactant 2

HCID 15870994Estra-1,3,5(10),16-tetraen-6-one-3-yl acetateHCID 21226445Aluminium lithium hydride2×

Product 1

HCID 15870995Estra-1,3,5(10),16-tetraen-3,6-diolYield 10%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of lithium aluminum hydride (LAH, 95%, 46.9 mg, 1.17 mmol) in 5 mL of anhydrous THF was added estra-1,3,5(10),16-tetraen-6-one-3-yl acetate, 6 (422.9 mg, 1.360 mmol) in 5 mL of anhydrous THF dropwise, with stirring. See FIG. 13. The reaction was stirred 50 min., after which further LAH (46.5 mg, 1.16 mmol) was added and the reaction stirred 22 h. After refluxing 4 h TLC still showed starting material. The reaction was quenched with 0.5 mL of water+0.5 mL of 20% (w/w) sulfuric acid and concentrated under reduced pressure. The residue was extracted four times with 10 mL portions of hot ethyl acetate and filtered through Celite. The combined filtrates were concentrated and purified twice by flash chromatography to give solid product (0.05 g, 0.2 mmol, 10%), m.p. 150-157° C.

Workup

  1. stirringThe reaction was stirred 50 min.
  2. stirringthe reaction stirred 22 h
  3. temperatureAfter refluxing 4 h TLC
  4. customThe reaction was quenched with 0.5 mL of water+0.5 mL of 20% (w/w) sulfuric acid
  5. concentrationconcentrated under reduced pressure
  6. extractionThe residue was extracted four times with 10 mL portions of hot ethyl acetate
  7. filtrationfiltered through Celite
  8. concentrationThe combined filtrates were concentrated
  9. custompurified twice by flash chromatography

Sources & evidence

ORD record
ord-0f1ba2956c0544859dde1afce6f1bc66
Source dataset
uspto-grants-2002_03
Patent number
US06352980B1

Reaction notes

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