Hydrogen Peroxide → 1alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(R)-(3-hydroxy-3-methylbutyloxy)pregna-5,7,16-triene

HRID 635030Notes

Reaction equation

HRID 635030 reaction equation
[C:1]([Si:5]([CH3:38])([CH3:37])[O:6][C@@H:7]1[C@@:26]2([CH3:27])[C:11](=[CH:12][CH:13]=[C:14]3[C@@H:25]2[CH2:24][CH2:23][C@@:22]2([CH3:28])[C@H:15]3[CH2:16][CH:17]=[C:18]2[C@H:19]([OH:21])[CH3:20])[CH2:10][C@@H:9]([O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[CH2:8]1)([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].Br[CH2:42][CH:43]1[O:47][C:44]1([CH3:46])[CH3:45].C([BH-](C(CC)C)C(CC)C)(CC)C.[Li+].[OH-].[Na+].OO>O1CCCC1.C(OCC)(=O)C>[Si:5]([O:6][C@@H:7]1[C@@:26]2([CH3:27])[C:11](=[CH:12][CH:13]=[C:14]3[C@@H:25]2[CH2:24][CH2:23][C@@:22]2([CH3:28])[C@H:15]3[CH2:16][CH:17]=[C:18]2[C@H:19]([O:21][CH2:42][CH2:43][C:44]([OH:47])([CH3:46])[CH3:45])[CH3:20])[CH2:10][C@@H:9]([O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:31])[CH3:32])[CH2:8]1)([C:1]([CH3:3])([CH3:2])[CH3:4])([CH3:38])[CH3:37]

Participants

9

Reactant 6

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 3611392Lithium tri-s-butylborohydrideHCID 110410611-bromo-2,3-epoxy-3-methylbutaneHCID 120200831alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(R)-hydroxypregna-5,7,16-triene

Product 1

HCID 120200841alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(R)-(3-hydroxy-3-methylbutyloxy)pregna-5,7,16-trieneYield 83%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A mixed solution of 1α,3β-bis(tert-butyldimethyl-silyloxy)-20(R)-hydroxypregna-5,7,16-triene (51 mg, 0.0911 mmol), sodium hydride (50 mg, 2.08 mmol) and 4-bromo-2,3-epoxy-2-methylbutane (75 mg, 0.455 mmol) in tetrahydrofuran (2ml) was heated under reflux for 1.5 hours and combined with 1M lithium tri-s-butylborohydride solution in tetrahydrofuran (0.9 ml, 0.900 mmol), and the mixed solution was heated under reflux for 20 minutes. The reaction solution was stirred with 3N aqueous sodium hydroxide solution and 30% aqueous hydrogen peroxide at room temperature for 30 minutes, then diluted with ethyl acetate, washed with brine and dried over magnesium sulfate. The solvent was distilled off under reduced pressure and the resulting residue was purified by preparative thin layer chromatography (0.5 mm×1, hexane:ethyl acetate=10:1, developed twice) to give the title compound as a colorless oil (48.6 mg, 83%).

Workup

  1. temperatureunder reflux for 1.5 hours
  2. temperaturethe mixed solution was heated
  3. temperatureunder reflux for 20 minutes
  4. washwashed with brine
  5. dry with materialdried over magnesium sulfate
  6. distillationThe solvent was distilled off under reduced pressure
  7. customthe resulting residue was purified by preparative thin layer chromatography (0.5 mm×1, hexane

Sources & evidence

ORD record
ord-be2b36357864425db4445d19c068b83f
Source dataset
uspto-grants-2001_02
Patent number
US06184398B2

Reaction notes

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