Tetrabutylammonium Fluoride → 1alpha,3beta-dihydroxy-20(S)-(3-hydroxy-3-methylbutylthio)pregna-5,7,16-triene

HRID 1268500Notes

Reaction equation

HRID 1268500 reaction equation
[Si]([O:8][C@@H:9]1[C@@:34]2([CH3:35])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:33]2[CH2:32][CH2:31][C@@:30]2([CH3:36])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C@@H:21]([S:23][CH2:24][CH2:25][C:26]([OH:29])([CH3:28])[CH3:27])[CH3:22])[CH2:12][C@@H:11]([OH:37])[CH2:10]1)(C(C)(C)C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>O1CCCC1.C(OCC)(=O)C>[OH:8][C@@H:9]1[C@@:34]2([CH3:35])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:33]2[CH2:32][CH2:31][C@@:30]2([CH3:36])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C@@H:21]([S:23][CH2:24][CH2:25][C:26]([OH:29])([CH3:27])[CH3:28])[CH3:22])[CH2:12][C@@H:11]([OH:37])[CH2:10]1

Participants

5

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 12019513HCID 12019513, compound

Product 1

HCID 120195191alpha,3beta-dihydroxy-20(S)-(3-hydroxy-3-methylbutylthio)pregna-5,7,16-trieneYield 90.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 1α-(tert-butyldimethylsilyloxy)-3β-hydroxy-20(S)-(3-hydroxy-3-methylbutylthio)pregna-5,7,16-triene (58.5 mg, 0.107 mmol) in tetrahydrofuran (3 ml) was added 1M tetra-n-butylammonium fluoride solution in tetrahydrofuran (2 ml), and the mixed solution was heated under reflux for 4 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate, and washed with ice-cooled 0.5 N hydrochloric acid, saturated aqueous sodium bicarbonate solution and brine successively, and the organic layer was dried over magnesium sulfate. The solvent was removed under reduced pressure, and the resulting residue was purified by preparative thin layer chromatography (0.5 mm×2, dichloromethane:ethanol=7:1, developed once) to give the title compound as a pale yellow oil (41.8 mg, 90%).

Workup

  1. temperaturethe mixed solution was heated
  2. temperatureunder reflux for 4 hours
  3. customAfter completion of the reaction
  4. washwashed with ice-
  5. temperaturecooled 0.5 N hydrochloric acid, saturated aqueous sodium bicarbonate solution and brine successively
  6. dry with materialthe organic layer was dried over magnesium sulfate
  7. customThe solvent was removed under reduced pressure
  8. customthe resulting residue was purified by preparative thin layer chromatography (0.5 mm×2, dichloromethane

Sources & evidence

ORD record
ord-c07779ed90c542659c206778b3b4643c
Source dataset
uspto-grants-2003_04
Patent number
US06555699B2

Reaction notes

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