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

HRID 635030Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 635030
[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]

Komponenten

9

Edukt 6

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 3611392Lithium tri-s-butylborohydrideHCID 110410613-(Bromomethyl)-2,2-dimethyloxiraneHCID 120200831alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(R)-hydroxypregna-5,7,16-triene

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

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%).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-be2b36357864425db4445d19c068b83f
Quelldatensatz
uspto-grants-2001_02
Patentnummer
US06184398B2

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