Hydrogen Peroxide → HCID 178455048, compound

HRID 585646Notes

Reaction equation

HRID 585646 reaction equation
[C:1]([Si:5]([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH:15]2[CH2:20][CH2:19][C:18](=[CH2:21])[CH2:17][CH2:16]2)=[C:11]([O:22][Si:23]([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24])[CH:10]=1)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].C12BC(CCC1)CCC2.OO.[OH-].[Na+].S(S([O-])(=O)=O)([O-])(=O)=[O:44].[Na+].[Na+]>C1COCC1>[Si:23]([O:22][C:11]1[CH:10]=[C:9]([O:8][Si:5]([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:6])[CH3:7])[CH:14]=[CH:13][C:12]=1[C@@H:15]1[CH2:16][CH2:17][C@H:18]([CH2:21][OH:44])[CH2:19][CH2:20]1)([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:24])[CH3:25]

Participants

7

Reactant 5

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 789669-Borabicyclo(3.3.1)nonaneHCID 146045Sodium dithionateHCID 17946008Tert-butyl[5-{[tert-butyl(dimethyl)silyl]oxy}-2-(4-methylenecyclohexyl)phenoxy]dimethylsilane

Product 1

HCID 178455048HCID 178455048, compoundYield 52%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

tert-Butyl[3-{[tert-butyl(dimethyl)silyl]oxy}-4-(4-methylenecyclohexyl)phenoxy]dimethyl silane (135 mg) was dissolved in anhydrous THF (5 ml) with stirring and cooled to −78° C. 9-Borabicyclo[3.3.1]nonane (3.13 ml, 0.5M in THF) was added to the stirred solution and the resulting reaction mixture allowed to warm to room temperature over 3 hr and then stirred for 3 days. Cooling to 0° C. was followed by addition of hydrogen peroxide (1 ml, 30% aqueous solution) and sodium hydroxide (1 ml, 2M aqueous solution). The reaction mixture was allowed to warm to room temperature with stirring over 1 hr, cooled to 0° C., and saturated aqueous sodium metabisulphate solution (30 ml) was added. The layers were separated and the aqueous layer extracted with ethyl acetate (3×20 ml). The combined organic phases were washed with brine (20 ml), dried over anhydrous magnesium sulphate, and concentrated in vacuo. Purification via flash column chromatography (SiO2 eluting with petroleum ether:diethyl ether, 3:17 v/v) afforded the desired product as a yellow oil (73 mg, 52%). δH (CDCl3): 0.18 (6H, s), 0.22 (6H, s), 0.97 (9H, s), 1.00 (9H, s), 1.03-1.15 (0.5H, m), 1.22-1.33 (0.5H, m), 1.43-1.61 (4H, m), 1.77-1.94 (4H, m), 2.75-2.92 (1H, m), 3.47 (1H, d), 3.70 (1H, d), 6.26-6.29 (1H, m), 6.37-6.40 (1H, m), 6.93-6.97 (1H, m).

Workup

  1. customthe resulting reaction mixture
  2. temperatureto warm to room temperature over 3 hr
  3. stirringstirred for 3 days
  4. temperatureCooling to 0° C.
  5. temperatureto warm to room temperature
  6. stirringwith stirring over 1 hr
  7. temperaturecooled to 0° C.
  8. customThe layers were separated
  9. extractionthe aqueous layer extracted with ethyl acetate (3×20 ml)
  10. washThe combined organic phases were washed with brine (20 ml)
  11. dry with materialdried over anhydrous magnesium sulphate
  12. concentrationconcentrated in vacuo
  13. customPurification via flash column chromatography (SiO2 eluting with petroleum ether:diethyl ether, 3:17 v/v)

Sources & evidence

ORD record
ord-167aa8ae8ea442419175105f9aef78c4
Source dataset
uspto-grants-2005_08
Patent number
US06933319B2

Reaction notes

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