Water → 2,3-dimethylene-1-phenyl-8-oxa-bicyclo[3.2.1]octane

HRID 10902Notes

Reaction equation

HRID 10902 reaction equation
C(OCC)C.O[CH:7]([CH2:18][C:19]([CH2:22][Si](C)(C)C)=[C:20]=[CH2:21])[CH2:8][CH2:9][C:10]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:11].[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C.O>CCOC(C)=O>[CH2:21]=[C:20]1[C:19](=[CH2:22])[CH2:18][CH:7]2[O:11][C:10]1([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:9][CH2:8]2

Participants

6

Reactant 4

HCID 962WaterHCID 3283Diethyl EtherHCID 65367Trimethylsilyl triflateHCID 121566794-Hydroxy-1-phenyl-6-trimethylsilanylmethyl-octa-6.7-diene-1-one

Product 1

HCID 113678442,3-dimethylene-1-phenyl-8-oxa-bicyclo[3.2.1]octaneYield 96.8%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

1.50 mL of diethyl ether was added to 4-hydroxy-1-phenyl-6-trimethylsilanylmethyl-octa-6.7-diene-1-one (110 mg, 0.36 mmol) under nitrogen atmosphere. While stirring at −78° C., TMSOTf (64.7 μL, 0.36 mmol) was added. While stirring the reaction mixture, the reaction temperature was slowly increased to room temperature for 3 hours. The reaction mixture was stirred at room temperature for 30 minutes. After the reaction was completed, H2O was added. After stirring for about 5 minutes, the reaction mixture was diluted with EtOAc and washed with water and saturated brine. The organic layer was separated from the reaction mixture and dried with anhydrous MgSO4. The solvent was removed under reduced pressure and the remaining material was purified with column chromatography (EtOAc/n-hexane=1/5) to obtain 74 mg of the product (96%).

Workup

  1. stirringWhile stirring the reaction mixture
  2. temperaturethe reaction temperature was slowly increased to room temperature for 3 hours
  3. stirringThe reaction mixture was stirred at room temperature for 30 minutes
  4. stirringAfter stirring for about 5 minutes
  5. washwashed with water and saturated brine
  6. customThe organic layer was separated from the reaction mixture
  7. dry with materialdried with anhydrous MgSO4
  8. customThe solvent was removed under reduced pressure
  9. customthe remaining material was purified with column chromatography (EtOAc/n-hexane=1/5)

Sources & evidence

ORD record
ord-ca52429c7d944b719557a85bafc3b396
Source dataset
uspto-grants-2006_08
Patent number
US07094913B2

Reaction notes

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