Hydrogen Peroxide → HCID 69629902, compound

HRID 1792201Notes

Reaction equation

HRID 1792201 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@:29]2([CH3:30])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:31])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C:21]([OH:24])([CH3:23])[CH3:22])[CH2:12][C@@H:11]([O:32][Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[H-].[Na+].Br[CH2:43][CH:44]1[O:48][C:45]1([CH3:47])[CH3:46].CCC(C)[BH-](C(C)CC)C(C)CC.[Li+].O1CCCC1.[OH-].[Na+].OO>O1CCCC1.C(OCC)(=O)C>[Si:1]([O:8][C@@H:9]1[C@@:29]2([CH3:30])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:31])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C:21]([O:24][CH2:43][CH2:44][C:45]([OH:48])([CH3:47])[CH3:46])([CH3:23])[CH3:22])[CH2:12][C@@H:11]([O:32][Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:34])[CH3:35])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

9

Reactant 6

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 110410611-bromo-2,3-epoxy-3-methylbutaneHCID 696299251alpha,3beta-Bis(tert-butyldimethylsilyloxy)-20-hydroxy-20-methylpregna-5,7,16-trieneHCID 131725857L-SELECTRIDE tetrahydrofuran

Product 1

HCID 69629902HCID 69629902, compoundYield 93.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 1α,3β-bis(tert-butyldimethylsilyloxy)-20-hydroxy-20-methylpregna-5,7,16-triene (67.7 mg, 0.118 mmol), sodium hydride (60% in oil, 40.0 mg, 1.00 mmol) and 1-bromo-2,3-epoxy-3-methylbutane (100 mg, 0.606 mmol) in tetrahydrofuran (1 ml) was refluxed under heating for 1.5 hours. To the thus obtained reaction solution, was added 1.0M L-SELECTRIDE/tetrahydrofuran solution (1.2 ml, 1.2 mmol) at room temperature, followed by stirring at the same temperature for 12 hours. After cooling the reaction solution with ice, a 3N aqueous sodium hydroxide solution and then hydrogen peroxide solution were added to the reaction solution. Immediately after the addition, the mixture was diluted with ethyl acetate and washed with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and evaporated to remove the solvent under reduced pressure; the thus obtained residue was purified by preparative thin layer chromatography (2 sheets (each 0.5 mm thickness), hexane:ethyl acetate=15:1, developed once) to give the titled compound (72.5 mg, 93%) as a colorless oil.

Workup

  1. temperatureunder heating for 1.5 hours
  2. customTo the thus obtained reaction solution
  3. temperatureAfter cooling the reaction solution with ice
  4. additionImmediately after the addition
  5. washwashed with water and saturated brine
  6. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  7. customevaporated
  8. customto remove the solvent under reduced pressure
  9. customthe thus obtained residue was purified by preparative thin layer chromatography (2 sheets (each 0.5 mm thickness), hexane

Sources & evidence

ORD record
ord-fcbac95b81c24dac8b57a9b0f6fda1a1
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

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