N,N-Dimethylacrylamide → 1alpha,3beta-bis(tert-butyldimethylsilyloxy)-17-(N,N-dimethylaminocarbonylethoxymethyl)androsta-5,7,16-triene

HRID 1792202Notes

Reaction equation

HRID 1792202 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][OH:29])[CH2:12][C@@H:11]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[H-].[Na+].[CH3:40][N:41]([CH3:46])[C:42](=[O:45])[CH:43]=[CH2:44].[Cl-].[NH4+]>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][CH2:44][CH2:43][C:42]([N:41]([CH3:46])[CH3:40])=[O:45])[CH2:12][C@@H:11]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:32])[CH3:33])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 17587N,N-DimethylacrylamideHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 673014381alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(hydroxymethyl)androsta-5,7,16-triene

Product 1

HCID 673012321alpha,3beta-bis(tert-butyldimethylsilyloxy)-17-(N,N-dimethylaminocarbonylethoxymethyl)androsta-5,7,16-trieneYield 93.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 1α,3β-bis(tert-butyldimethylsilyloxy)-17-hydroxymethylandrosta-5,7,16-triene (951 mg, 1.75 mmol) in tetrahydrofuran (17.5 ml), was added sodium hydride (60% in oil, 105 mg, 2.62 mmol), followed by stirring under nitrogen stream at room temperature for 30 min. After adding N,N-dimethylacrylamide (540 mg, 5.44 mmol), the solution was stirred at 5° C. for 14 hours, poured into a saturated aqueous ammonium chloride solution, extracted with ethyl acetate (3 times) and washed with saturated brine and water. 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 column chromatography (hexane:ethyl acetate 2:1) to give the titled compound (1.05 g, 92.7%) as a yellow oil.

Workup

  1. stirringthe solution was stirred at 5° C. for 14 hours
  2. extractionextracted with ethyl acetate (3 times)
  3. washwashed with saturated brine and water
  4. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  5. customevaporated
  6. customto remove the solvent under reduced pressure
  7. customthe thus obtained residue was purified by column chromatography (hexane:ethyl acetate 2:1)

Sources & evidence

ORD record
ord-535b11fdc0c14b828a6d5ca418dab416
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

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