Hydrogen Peroxide → Tetrahydro-3'R,5'R-dibenzoyloxy-6'S-methyl-2H-pyrane

HRID 2104227Notes

Reaction equation

HRID 2104227 reaction equation
[C:1]([O:9][C@@H:10]1[CH2:16][C@@H:15]([O:17][C:18](=[O:25])[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@H:14]([CH3:26])[O:13][C:11]1=[O:12])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([BH2-]CCC(C)C)CC(C)C.OO.[OH-].[Na+]>C1COCC1.O>[C:1]([O:9][C@@H:10]1[CH2:16][C@@H:15]([O:17][C:18](=[O:25])[C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C@H:14]([CH3:26])[O:13][CH:11]1[OH:12])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 11473679(2S,3R,5R)-2-methyl-6-oxotetrahydro-2H-pyran-3,5-diyl dibenzoateHCID 131727586Diisoamylborohydride

Product 1

HCID 16066478Tetrahydro-3'R,5'R-dibenzoyloxy-6'S-methyl-2H-pyraneYield 93.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

The compound (IX) (5 g, 14.11 mmol) dissolved in dry THF (15 ml) is added to 0.5M Diisoamylborohydride (127 ml) prepared in the reaction (1). Then, it is stirred for 20 hours at a room temperature. After the reaction is finished, water (3 ml) is added and then stirred for 30 minutes. The reaction mixture is cooled to 0° C., and then 30% H2O2 (15 ml) is added and 3N NaOH is added to maintain the pH 7-8. The solvent THF is vacuum concentrated, and then it is dissolved in CH2Cl2 (100 ml) and washed by water (50 ml). An organic layer is dried using anhydrous MgSO4. The solution is vacuum concentrated, and then the compound (II) (4.72 g, 93.8%, α:β=4.6:1) is isolated using flash column chromatography (toluene/EtOAc, 10:1, v/v).

Workup

  1. stirringstirred for 30 minutes
  2. temperatureThe reaction mixture is cooled to 0° C.
  3. temperatureto maintain the pH 7-8
  4. concentrationconcentrated
  5. dissolutionit is dissolved in CH2Cl2 (100 ml)
  6. washwashed by water (50 ml)
  7. customAn organic layer is dried
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-a6ab7491b1bc4565b276836679538df4
Source dataset
uspto-grants-2009_08
Patent number
US07576225B2

Reaction notes

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