(Dimethyl sulfide)trihydroboron → [2-(benzyloxy)-5-((1R)-2-bromo-1-{[tert-butyl(dimethyl)silyl]oxy}ethyl)phenyl]methanol

HRID 916068Notes

Reaction equation

HRID 916068 reaction equation
CSC.B.C[O:6][C:7](=O)[C:8]1[CH:13]=[C:12]([C@@H:14]([O:17][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19])[CH2:15][Br:16])[CH:11]=[CH:10][C:9]=1[O:25][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>O1CCCC1>[CH2:26]([O:25][C:9]1[CH:10]=[CH:11][C:12]([C@@H:14]([O:17][Si:18]([C:21]([CH3:22])([CH3:23])[CH3:24])([CH3:19])[CH3:20])[CH2:15][Br:16])=[CH:13][C:8]=1[CH2:7][OH:6])[C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1

Participants

4

Reactant 2

HCID 12423031(Dimethyl sulfide)trihydroboronHCID 57438683Methyl 2-(benzyloxy)-5-((1R)-2-bromo-1-{[tert-butyl(dimethyl)silyl]oxy]ethyl)benzoate

Product 1

HCID 12988834[2-(benzyloxy)-5-((1R)-2-bromo-1-{[tert-butyl(dimethyl)silyl]oxy}ethyl)phenyl]methanolYield 80.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Borane dimethylsulfide complex (42.4 ml of 10M solution in tetrahydrofuran, 424 mmol) was added dropwise to a solution methyl-2-(benzyloxy)-5-((1R)-2-bromo-1-{[tert-butyl(dimethyl)silyl]oxy}ethyl)benzoate (Preparation 40) (91.0 g, 189 mmol) in tetrahydrofuran (1600 ml). The resulting mixture was then heated to reflux for 2 hours and then cooled to 0° C. before quenching with methanol (270 ml). The mixture was left to stir at room temperature for 16 hours and then the solvent removed in vacuo. The residue was partitioned between dichloromethane (500 ml) and water (500 ml). The aqueous phase was separated and extracted with dichloromethane (500 ml) and the combined organic extracts washed with brine (500 ml), dried (magnesium sulfate) and the solvent removed in vacuo. The residue was purified by flash column chromatography on silica gel eluting with cyclohexane:ethyl acetate (100:0 changing to 80:20, by volume) to give the title compound (68.7 g) as a colourless oil.

Workup

  1. temperatureThe resulting mixture was then heated
  2. temperatureto reflux for 2 hours
  3. custombefore quenching with methanol (270 ml)
  4. waitThe mixture was left
  5. customthe solvent removed in vacuo
  6. customThe residue was partitioned between dichloromethane (500 ml) and water (500 ml)
  7. customThe aqueous phase was separated
  8. extractionextracted with dichloromethane (500 ml)
  9. washthe combined organic extracts washed with brine (500 ml)
  10. dry with materialdried (magnesium sulfate)
  11. customthe solvent removed in vacuo
  12. customThe residue was purified by flash column chromatography on silica gel eluting with cyclohexane:ethyl acetate (100:0 changing to 80:20, by volume)

Sources & evidence

ORD record
ord-84aadd6ca3fa453b8ce9b174a59bf4fa
Source dataset
uspto-grants-2007_09
Patent number
US07268147B2

Reaction notes

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