Hydrogen Peroxide → HCID 20726820, compound

HRID 460465Notes

Reaction equation

HRID 460465 reaction equation
C([Li])CCC.C[C:7]([CH3:10])([O-:9])[CH3:8].[K+].C(NC(C)C)(C)C.[O:19]([C@H:27]1[CH2:32][CH2:31][C@H:30]2[C@H:33]3[C@H:42]([CH2:43][CH2:44][C@:28]12[CH3:29])[C:41]1C=[CH:39][C:38]([O:45][CH3:46])=[CH:37][C:36]=1CC3)[Si:20]([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:22])[CH3:21].B(OC)(OC)OC.OO.S([O-])([O-])(=O)=S.[Na+].[Na+]>O1CCCC1>[O:19]([C@H:27]1[CH2:32][CH2:31][C@H:30]2[C@H:33]3[C@H:42]([CH2:43][CH2:44][C@:28]12[CH3:29])[C:41]1[CH:36]=[CH:37][C:38]([O:45][CH3:46])=[CH:39][C:10]=1[CH:7]([OH:9])[CH2:8]3)[Si:20]([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:21])[CH3:22]

Participants

9

Reactant 7

HCID 784Hydrogen PeroxideHCID 7912DiisopropylamineHCID 8470Trimethyl borateHCID 24477Sodium ThiosulfateHCID 1383178717beta-(t-Butyldimethylsiloxy)-3-methoxyestra-1,3,5(10)-trieneHCID 23665647Potassium tert-butoxideHCID 178418339Butyllithium

Product 1

HCID 20726820HCID 20726820, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

n-Butyllithium (2.5 M in hexane, 40 ml, 100 mmol) was added to potassium tert-butoxide (1M in tetrahydrofuran, 100 ml, 100 mmol) at −70° C. under nitrogen atmosphere, followed by addition of diisopropylamine (19.1 g, 100 mmol) at the same temperature. After the mixture was stirred for 10 minutes, 17β-(t-butyldimethylsiloxy)-3-methoxyestra-1,3,5(10)-triene (10 g, 25 mmol) synthesized by the method described in Tetrahedron Lett., 3223 (1988) and dissolved in tetrahydrofuran (40 ml) was added dropwise at −70° C. over 10 to 15 minutes, and the resulting mixture was stirred for 4 hours. Trimethyl borate (15.6 g, 150 mmol) was added to the reaction mixture, which was then warmed to ice cold temperature and stirred for 1 hour and further stirred with 30% hydrogen peroxide (35 ml) for 1 hour at room temperature. The reaction mixture was cooled again on ice and 10% aqueous sodium thiosulfate (150 ml) was added to stop the reaction. After the reaction mixture was extracted with ether, the organic layer was washed with water and saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and then filtered. After distilling off the solvent, the residue was purified by silica gel flash chromatography (eluent: hexane/ethyl acetate=5/1→3/1) to give 17β-(t-butyl-dimethylsiloxy)-3-methoxyestra-1,3,5(10)-trien-6-ol (8.38 g, Yield 82%).

Workup

  1. additionwas added dropwise at −70° C. over 10 to 15 minutes
  2. stirringthe resulting mixture was stirred for 4 hours
  3. temperaturewas then warmed to ice cold temperature
  4. stirringstirred for 1 hour
  5. additionwas added
  6. customthe reaction
  7. extractionAfter the reaction mixture was extracted with ether
  8. washthe organic layer was washed with water and saturated aqueous sodium chloride
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationfiltered
  11. distillationAfter distilling off the solvent
  12. customthe residue was purified by silica gel flash chromatography (eluent: hexane/ethyl acetate=5/1→3/1)

Sources & evidence

ORD record
ord-7f79e0446a444ad3b202696b616445cc
Source dataset
uspto-grants-2007_03
Patent number
US07196081B2

Reaction notes

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