Hydrogen Peroxide → 1alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(3-hydroxy-3-methylbutoxymethyl)androsta-5,7,16-triene

HRID 1792199Notes

Reaction equation

HRID 1792199 reaction equation
CCC(C)[BH-](C(C)CC)C(C)CC.[Li+].[Si:15]([O:22][C@@H:23]1[C@@:40]2([CH3:41])[C:27](=[CH:28][CH:29]=[C:30]3[C@@H:39]2[CH2:38][CH2:37][C@@:35]2([CH3:36])[C@H:31]3[CH2:32][CH:33]=[C:34]2[CH2:42][O:43][CH2:44][CH:45]2[O:49][C:46]2([CH3:48])[CH3:47])[CH2:26][C@@H:25]([O:50][Si:51]([C:54]([CH3:57])([CH3:56])[CH3:55])([CH3:53])[CH3:52])[CH2:24]1)([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16].[OH-].[Na+].OO>O1CCCC1.C(OCC)(=O)C>[Si:15]([O:22][C@@H:23]1[C@@:40]2([CH3:41])[C:27](=[CH:28][CH:29]=[C:30]3[C@@H:39]2[CH2:38][CH2:37][C@@:35]2([CH3:36])[C@H:31]3[CH2:32][CH:33]=[C:34]2[CH2:42][O:43][CH2:44][CH2:45][C:46]([OH:49])([CH3:47])[CH3:48])[CH2:26][C@@H:25]([O:50][Si:51]([C:54]([CH3:57])([CH3:56])[CH3:55])([CH3:52])[CH3:53])[CH2:24]1)([C:18]([CH3:21])([CH3:19])[CH3:20])([CH3:17])[CH3:16]

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 3611392Lithium tri-s-butylborohydride2×HCID 86760153HCID 86760153, compound

Product 1

HCID 696305481alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(3-hydroxy-3-methylbutoxymethyl)androsta-5,7,16-trieneYield 87%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Procedure

At room temperature, a solution of 1.0M L-SELECTRIDE in tetrahydrofuran (0.25 ml, 0.25 mmol) was added to a solution of 1α,3β-bis(tert-butyldimethylsilyloxy)-17-(2,3-epoxy-3-methylbutoxymethyl)androsta-5,7,16-triene (48.3 mg, 0.0768 mmol) in tetrahydrofuran (2 ml) and stirred at the same temperature for 1 hour. To the solution, was further added a solution of 1.0M L-SELECTRIDE in tetrahydrofuran (0.2 ml, 0.2 mmol), followed by stirring at the same temperature for 1 hour. After cooling the reaction solution with ice, a 3N aqueous sodium hydroxide solution and then hydrogen peroxide solution were added. 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 (1 sheet (0.5 mm thickness), hexane:ethyl acetate=10:1, developed twice) to give the titled compound (42.0 mg, 87%) as a colorless oil.

Workup

  1. stirringby stirring at the same temperature for 1 hour
  2. temperatureAfter cooling the reaction solution with ice
  3. additionImmediately after the addition
  4. washwashed with water and saturated brine
  5. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  6. customevaporated
  7. customto remove the solvent under reduced pressure
  8. customthe thus obtained residue was purified by preparative thin layer chromatography (1 sheet (0.5 mm thickness), hexane

Sources & evidence

ORD record
ord-c7fd4f7d8e38425ba62bc91da9c29ed4
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

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