Hydrogen Peroxide → HCID 11984447, compound

HRID 2371499Notes

Reaction equation

HRID 2371499 reaction equation
[Si:1]([O:18][CH2:19][C@@H:20]([OH:32])[CH2:21][C:22](=[O:31])[CH2:23][C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(B(CC)OC)C.[BH4-].[Na+].OO.P([O-])([O-])([O-])=O>O1CCCC1.C(Cl)Cl.C(OCC)(=O)C.CO>[Si:1]([O:18][CH2:19][C@@H:20]([OH:32])[CH2:21][C@@H:22]([OH:31])[CH2:23][C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])([C:14]([CH3:17])([CH3:15])[CH3:16])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

9

Reactant 5

HCID 784Hydrogen PeroxideHCID 1061PhosphateHCID 522516DiethylmethoxyboraneHCID 4311764Sodium borohydrideHCID 11984446HCID 11984446, compound

Product 1

HCID 11984447HCID 11984447, compoundYield 76%

Reagents, catalysts & solvents 3

HCID 887MethanolSolvent2×HCID 8028TetrahydrofuranSolvent2×HCID 21226138Dichloromethane ethylacetateSolvent

Conditions

Temperature
-70 °C

Procedure

To a solution containing 52.53 g (0.115 mol) of tert-butyl (5S)-6-tert-butyldiphenylsilyloxy-5-hydroxy-3-oxohexanoate, 800 ml of anhydrous tetrahydrofuran and 200 ml of anhydrous methanol was added 126 ml (0.126 mol) of a 1 M solution of diethyl methoxy borane in tetrahydrofuran with stirring at -70° C. After stirring the mixture for 1 hour at -65° C., thereto was added 5.66 g (0.15 mol) of sodium borohydride and the mixture was reacted for 4 hours at the same temperature. The reactant was added dropwise to the mixture of 425 ml of 30% hydrogen peroxide, 850 ml of 0.2 M phosphate buffer solution (pH 7.0 ) and 850 ml of methanol at -20° to -10° C. Further after stirring the mixture for a half hour at room temperature, the mixture was concentrated under reduced pressure. The concentrated solution was extracted with methylene chloride, and the methylene chloride layer was washed with water, then dried and distilled away under reduced pressure. The residue was purified by subjecting to silica gel column chromatography [eluent: methylene chloride-ethyl acetate (10:1)]to give 40.1 g of tert-butyl (3R,5S)-6-tert-butyldiphenylsilyloxy-3,5-dihydroxyhexanoate as syrups (yield: 75%).

Workup

  1. stirringAfter stirring the mixture for 1 hour at -65° C.
  2. customthe mixture was reacted for 4 hours at the same temperature
  3. stirringFurther after stirring the mixture for a half hour at room temperature
  4. concentrationthe mixture was concentrated under reduced pressure
  5. extractionThe concentrated solution was extracted with methylene chloride
  6. washthe methylene chloride layer was washed with water
  7. customdried
  8. distillationdistilled away under reduced pressure
  9. customThe residue was purified

Sources & evidence

ORD record
ord-a60f177ea99d45a5b976a04b0bb51108
Source dataset
uspto-grants-1992_03
Patent number
US05093363

Reaction notes

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