Water → 1alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(2-hydroxy-2-methylpropoxymethyl)androsta-5,7,16-triene

HRID 1792208Notes

Reaction equation

HRID 1792208 reaction equation
[Si:1]([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]C(OC(C)(C)C)=O)[CH2:12][C@@H:11]([O:38][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH3:46][Mg]Br.[O:49]1[CH2:53][CH2:52]CC1.[Cl-].[NH4+].O>O1CCCC1>[Si:1]([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][C:53]([OH:49])([CH3:52])[CH3:46])[CH2:12][C@@H:11]([O:38][Si:39]([C:42]([CH3:44])([CH3:45])[CH3:43])([CH3:40])[CH3:41])[CH2:10]1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 962WaterHCID 25517Ammonium ChlorideHCID 673017221alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(tert-butoxycarbonylmethoxymethyl)androsta-5,7,16-trieneHCID 178420675HCID 178420675, compound

Product 1

HCID 696309111alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(2-hydroxy-2-methylpropoxymethyl)androsta-5,7,16-trieneYield 70.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 1α,3β-bis(tert-butyldimethylsilyloxy)-17-(tert-butoxycarbonylmethoxymethyl)androsta-5,7,16-triene (175 mg, 0.266 mmol) in tetrahydrofuran (4 ml), was added dropwise a 0.93M methylmagnesium bromide/tetrahydrofuran solution (3 ml, 2.79 mmol) at external temperature of −30° C., followed by stirring at the same temperature for 1 hour and 30 min. At the same temperature, a saturated aqueous ammonium chloride solution was added to the reaction solution, which was then warmed to room temperature and stirred for 10 min. Water was added to the reaction solution, which was then extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium bicarbonate solution and saturated brine, 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 (3 sheets (each 0.5 mm thickness), hexane:ethyl acetate=20:1, developed twice, hexane:ethyl acetate=15:1, developed twice, and hexane:ethyl acetate 10:1, developed once) to give the titled compound (115.3 mg, 70%) as a colorless oil.

Workup

  1. stirringstirred for 10 min
  2. extractionwas then extracted with ethyl acetate
  3. washThe organic layer was washed with a saturated aqueous sodium bicarbonate solution and saturated brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customevaporated
  6. customto remove the solvent under reduced pressure
  7. customthe thus obtained residue was purified by preparative thin layer chromatography (3 sheets (each 0.5 mm thickness), hexane

Sources & evidence

ORD record
ord-09f817b1421040bf81adda1049ebfd49
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

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