Tetrahydrofuran → 1alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(3-ethyl-3-hydroxypentyloxymethyl)androsta-5,7,16-triene

HRID 1792203Notes

Reaction equation

HRID 1792203 reaction equation
Cl[Ce](Cl)Cl.[CH2:5]([Mg]Br)[CH3:6].[Si:9]([O:16][C@@H:17]1[C@@:34]2([CH3:35])[C:21](=[CH:22][CH:23]=[C:24]3[C@@H:33]2[CH2:32][CH2:31][C@@:29]2([CH3:30])[C@H:25]3[CH2:26][CH:27]=[C:28]2[CH2:36][O:37][CH2:38][CH2:39][C:40](N(C)C)=[O:41])[CH2:20][C@@H:19]([O:45][Si:46]([C:49]([CH3:52])([CH3:51])[CH3:50])([CH3:48])[CH3:47])[CH2:18]1)([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10].[Cl-].[NH4+].O1CC[CH2:57][CH2:56]1>>[Si:9]([O:16][C@@H:17]1[C@@:34]2([CH3:35])[C:21](=[CH:22][CH:23]=[C:24]3[C@@H:33]2[CH2:32][CH2:31][C@@:29]2([CH3:30])[C@H:25]3[CH2:26][CH:27]=[C:28]2[CH2:36][O:37][CH2:38][CH2:39][C:40]([CH2:5][CH3:6])([OH:41])[CH2:56][CH3:57])[CH2:20][C@@H:19]([O:45][Si:46]([C:49]([CH3:52])([CH3:51])[CH3:50])([CH3:48])[CH3:47])[CH2:18]1)([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10]

Participants

6

Reactant 5

HCID 8028Tetrahydrofuran2×HCID 25517Ammonium ChlorideHCID 161282Cerium trichlorideHCID 673012321alpha,3beta-bis(tert-butyldimethylsilyloxy)-17-(N,N-dimethylaminocarbonylethoxymethyl)androsta-5,7,16-trieneHCID 178418443HCID 178418443, compound

Product 1

HCID 696305011alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(3-ethyl-3-hydroxypentyloxymethyl)androsta-5,7,16-trieneYield 56%

Procedure

Tetrahydrofuran (11 ml) was mixed with anhydrous cerous (III) chloride (2.33 g, 9.46 mmol), stirred under nitrogen stream at room temperature for 30 min., cooled with ice, mixed with ethylmagnesium bromide (0.96 mol/l, 9.0 ml, 8.6 mmol) and stirred for 30 min. The reaction solution was mixed with a solution of 1α,3β-bis(tert-butyldimethylsilyloxy)-17-(N,N-dimethylaminocarbonylethoxymethyl)androsta-5,7,16-triene (553 mg, 0.86 mmol) in tetrahydrofuran (11 ml) at 0° C., followed by stirring for 1 hour at the same temperature. The reaction solution was poured into a saturated aqueous ammonium chloride solution, extracted with ethyl acetate (3 times), washed with saturated brine and water, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to remove solvent, giving a reaction mixture containing a ketone body. The thus obtained mixture was again subjected to the same reaction and worked up; the thus obtained residue was purified by column chromatography (hexane:ethyl acetate=5:1) to give the titled compound (317 mg, 56.0%) as a yellow oil.

Workup

  1. temperaturecooled with ice
  2. stirringstirred for 30 min
  3. stirringby stirring for 1 hour at the same temperature
  4. extractionextracted with ethyl acetate (3 times)
  5. washwashed with saturated brine and water
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customevaporated under reduced pressure
  8. customto remove solvent
  9. customgiving a reaction mixture
  10. customThe thus obtained mixture was again subjected to the same reaction
  11. customthe thus obtained residue was purified by column chromatography (hexane:ethyl acetate=5:1)

Sources & evidence

ORD record
ord-aa466e4402f844efbbd164d3cf1c23bb
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

Loading…