Hydrogen Peroxide → HCID 22467278, compound

HRID 1934563Notes

Reaction equation

HRID 1934563 reaction equation
[Si:1]([O:18][C:19]1[C:24]2[CH2:25][CH2:26][CH2:27][C:28]([CH2:30][OH:31])=[CH:29][C:23]=2[CH:22]=[CH:21][CH:20]=1)([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.[Si]([O:49]C1C2CCC=C(CO)CC=2C=CC=1)(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.B.O1CCCC1.[OH-].[Na+].OO>C1COCC1>[Si:1]([O:18][C:19]1[C:24]2[CH2:25][CH2:26][CH2:27][CH:28]([CH2:30][OH:31])[CH:29]([OH:49])[C:23]=2[CH:22]=[CH:21][CH:20]=1)([C:14]([CH3:15])([CH3:16])[CH3:17])([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

Participants

7

Reactant 5

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 2723981Borane;tetrahydrofuran2×HCID 22467281HCID 22467281, compoundHCID 22467284HCID 22467284, compound

Product 1

HCID 22467278HCID 22467278, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
5 °C

Procedure

To a solution of a mixture of [1-(tert-butyldiphenylsilyloxy)-8,9-dihydro-7H-benzocyclohepten-6-yl]methanol and [1-(tert-butyldiphenylsilyloxy)-8,9-dihydro-5H-benzocyclohepten-6-yl]methanol (1.10 g) in THF (10 ml) was added borane-tetrahydrofuran complex (1M THF solution, 7.71 ml) at −30 to −20° C. The mixture was stirred at the same temperature for 30 minutes, and then at room temperature for 18 hours. The reaction mixture was cooled to 5° C. After addition of borane-tetrahydrofuran complex (1M THF solution, 2.57 ml), the mixture was stirred at room temperature for 3 hours. After addition of 2N NaOH solution (2.59 ml) and 30% H2O2 solution (1.76 ml) at 5° C., the resultant was stirred at room temperature for 3 hours. The mixture was extracted with EtOAc. The organic layer was washed with water and then brine. It was dried over magnesium sulfate and evaporated in vacuo. The residue was purified by silica gel column chromatography (hexane-EtOAc 3:2 to 1:2) to give first (5RS,6RS)-1-(tert-butyldiphenylsilyloxy)-6-hydroxymethyl-6,7,8,9-tetrahydro-5H-benzocyclohepten-5-ol (719.8 mg) as an amorphous solid and then (6SR,7RS)-1-(tert-butyldiphenylsilyloxy)-6-hydroxymethyl-6,7,8,9-tetrahydro-5H-benzocyclohepten-7-ol (181.4 mg) as an amorphous solid.

Workup

  1. waitat room temperature for 18 hours
  2. stirringthe mixture was stirred at room temperature for 3 hours
  3. stirringthe resultant was stirred at room temperature for 3 hours
  4. extractionThe mixture was extracted with EtOAc
  5. washThe organic layer was washed with water
  6. dry with materialIt was dried over magnesium sulfate
  7. customevaporated in vacuo
  8. customThe residue was purified by silica gel column chromatography (hexane-EtOAc 3:2 to 1:2)

Sources & evidence

ORD record
ord-13fa5c3dee44430e8ed7be5365a37779
Source dataset
uspto-grants-2002_05
Patent number
US06384072B1

Reaction notes

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