Hexane → (S)-4-tert-butyldimethylsilyloxy-2-(2-tert-butyldimethylsilyloxyethoxy)-1-trityloxybutane

HRID 1168056Notes

Reaction equation

HRID 1168056 reaction equation
[H-].[Na+].CCCCCC.[Si:9]([O:16][CH2:17][CH2:18][C@H:19]([OH:41])[CH2:20][O:21][C:22]([C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10].CS(O[CH2:47][CH2:48][O:49][Si:50]([C:53]([CH3:56])([CH3:55])[CH3:54])([CH3:52])[CH3:51])(=O)=O>CS(C)=O.O>[Si:9]([O:16][CH2:17][CH2:18][C@H:19]([O:41][CH2:47][CH2:48][O:49][Si:50]([C:53]([CH3:56])([CH3:55])[CH3:54])([CH3:52])[CH3:51])[CH2:20][O:21][C:22]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)([C:29]1[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1)[C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1)([C:12]([CH3:14])([CH3:15])[CH3:13])([CH3:11])[CH3:10]

Participants

7

Reactant 4

HCID 8058HexaneHCID 24758Sodium hydrideHCID 12114686(S)-4-tert-butyldimethylsilyloxy-1-trityloxy-2-butanolHCID 229950482-Tert-butyldimethylsilyloxyethyl methanesulfonate

Product 1

HCID 12114687(S)-4-tert-butyldimethylsilyloxy-2-(2-tert-butyldimethylsilyloxyethoxy)-1-trityloxybutaneYield 55%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 962WaterSolvent

Procedure

Sodium hydride (2.11 g, 52.7 mmol, 60% in oil) was loaded under argon circumstance in three-necked flask and hexane (30 ml) was added thereto. After stirring for a while, it was allowed to stand and the supernatant was removed by syringe. By repeating this procedure three times, the oil of sodium hydride was removed. After drying in vacuo anhydrous dimethyl sulfoxide (DMSO) (10 ml) was added and the solution was stirred at 60° C. for 1 hour. After cooling to room temperature, (S)-4-tert-butyldimethylsilyloxy-1-trityloxy-2-butanol (20.36 g, 44.0 mol) in DMSO (12 ml) was gradually dropped at room temperature to the solution and then the solution was stirred for 30 minutes. To the solution was gradually dropped 2-tert-butyldimethylsilyloxyethyl methanesulfonate (12.28 g, 48.3 mol) in DMSO (12 ml) at room temperature and then the solution was stirred for 12 hours. To the reaction mixture was added water (40 ml) and the solution was extracted with ethyl acetate. The extract was washed with water (50 ml) twice and with saturated brine once, dried on sodium sulfate, filtered and condensed in vacuo. The residue was subjected to silica gel chromatography to give (S)-4-tert-butyldimethylsilyloxy-2-(2-tert-butyldimethylsilyloxyethoxy)-1-trityloxybutane (11.2 g, yield 55%).

Workup

  1. customthe supernatant was removed by syringe
  2. customthe oil of sodium hydride was removed
  3. dry with materialAfter drying in vacuo anhydrous dimethyl sulfoxide (DMSO) (10 ml)
  4. additionwas added
  5. stirringthe solution was stirred at 60° C. for 1 hour
  6. stirringthe solution was stirred for 30 minutes
  7. customat room temperature
  8. stirringthe solution was stirred for 12 hours
  9. extractionthe solution was extracted with ethyl acetate
  10. washThe extract was washed with water (50 ml) twice
  11. dry with materialwith saturated brine once, dried on sodium sulfate
  12. filtrationfiltered
  13. customcondensed in vacuo

Sources & evidence

ORD record
ord-22e6912049df44f89f9629de2d6d0761
Source dataset
uspto-grants-2003_09
Patent number
US06620977B1

Reaction notes

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