TBAF tetrahydrofuran → 1alpha,3beta-Dihydroxy-17-(4-hydroxy-4-methylpentyloxymethyl)androsta-5,7,16-triene

HRID 1792171Notes

Reaction equation

HRID 1792171 reaction equation
[Si]([O:8][C@@H:9]1[C@@:26]2([CH3:27])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:25]2[CH2:24][CH2:23][C@@:21]2([CH3:22])[C@H:17]3[CH2:18][CH:19]=[C:20]2[CH2:28][O:29][CH2:30][CH2:31][CH2:32][C:33]([O:36][Si](CC)(CC)CC)([CH3:35])[CH3:34])[CH2:12][C@@H:11]([O:44][Si](C(C)(C)C)(C)C)[CH2:10]1)(C(C)(C)C)(C)C.O1CCCC1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>O1CCCC1.C(OCC)(=O)C>[OH:8][C@@H:9]1[C@@:26]2([CH3:27])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:25]2[CH2:24][CH2:23][C@@:21]2([CH3:22])[C@H:17]3[CH2:18][CH:19]=[C:20]2[CH2:28][O:29][CH2:30][CH2:31][CH2:32][C:33]([OH:36])([CH3:35])[CH3:34])[CH2:12][C@@H:11]([OH:44])[CH2:10]1

Participants

5

Reactant 2

HCID 11078149TBAF tetrahydrofuranHCID 696308821alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(4-triethylsilyloxy-4-methylpentyloxymethyl)androsta-5,7,16-triene

Product 1

HCID 696302141alpha,3beta-Dihydroxy-17-(4-hydroxy-4-methylpentyloxymethyl)androsta-5,7,16-trieneYield 37%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 1α,3β-bis(tert-butyldimethylsilyloxy)-17-(4-triethylsilyloxy-4-methylpentyloxymethyl)androsta-5,7,16-triene (278.7 mg, 0.367 mmol) in tetrahydrofuran (2 ml), was added a 1M tetra-n-butylammonium fluoride tetrahydrofuran solution (3.3 ml, 3.3 mmol), followed by reflux under heating for 14 hours. The reaction solution was diluted with ethyl acetate, washed with 5% hydrochloric acid, a saturated aqueous sodium bicarbonate solution and saturated brine in that order, the organic layer was dried over anhydrous magnesium sulfate and evaporated under reduced pressure to remove the solvent. The thus obtained residue was purified by column chromatography (dichloromethane:ethanol=10:1) and preparative thin layer chromatography (4 sheets (each 0.5 mm thickness), dichloromethane:ethanol=20:1, developed twice, and then dichloromethane:ethanol=10:1, developed twice) to give the titled compound (56.3 mg, 37%) as a colorless foam.

Workup

  1. temperatureby reflux
  2. temperatureunder heating for 14 hours
  3. washwashed with 5% hydrochloric acid
  4. dry with materiala saturated aqueous sodium bicarbonate solution and saturated brine in that order, the organic layer was dried over anhydrous magnesium sulfate
  5. customevaporated under reduced pressure
  6. customto remove the solvent
  7. customThe thus obtained residue was purified by column chromatography (dichloromethane:ethanol=10:1) and preparative thin layer chromatography (4 sheets (each 0.5 mm thickness), dichloromethane

Sources & evidence

ORD record
ord-f7c5eced16ea4c7a87b6b951987b0272
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

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