Water → 2,3-dimethylene-1-phenyl-9-oxa-bicyclo[3.3.1]nonane

HRID 985730Notes

Reaction equation

HRID 985730 reaction equation
C(OCC)C.[OH:6][CH:7]([CH2:19][C:20]([CH2:23][Si](C)(C)C)=[C:21]=[CH2:22])[CH2:8][CH2:9][C:10](=O)[CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.FC(F)(F)S(O[Si](C)(C)C)(=O)=O.O>C(OCC)(=O)C>[CH2:22]=[C:21]1[C:20](=[CH2:23])[CH2:19][CH:7]2[O:6][C:11]1([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:10][CH2:9][CH2:8]2

Participants

6

Reactant 4

HCID 962WaterHCID 3283Diethyl EtherHCID 65367Trimethylsilyl triflateHCID 22507801HCID 22507801, compound

Product 1

HCID 114701772,3-dimethylene-1-phenyl-9-oxa-bicyclo[3.3.1]nonaneYield 98%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

1.50 mL of diethyl ether was added to 5-hydroxy-1-phenyl-7-trimethylsilanylmethyl-nona-7,8-diene-2-one (117 mg, 0.37 mmol) under nitrogen atmosphere. While stirring at −78° C., trimethylsilyl trifluoromethanesulfonate (TMSOTf; 67 μL, 0.37 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 ethyl acetate (EtOAc) and washed with water and saturated brine. The organic layer was separated from the reaction mixture and dried with anhydrous magnesium sulfate (MgSO4). The solvent was removed under reduced pressure and the remaining material was purified with column chromatography (EtOAc/n-hexane={fraction (1/7)}) to obtain 82 mg of the product (98%). 1H NMR(300 MHz, CDCl3) δ 7.43 (d, 2H, J=1.5 Hz), 7.21 (m, 3H), 5.17 (s, 1H), 5.07 (s, 1H), 4.72 (s, 1H), 4.33 (s, 1H), 4.13 (s, 1H), 3.00 (m, 1H), 2.40 (d, 1H, J=14.8 Hz), 2.19 (m, 2H), 1.94 (m, 2H), 1.60 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 152.5, 147.0, 146.0, 128.2, 127.4, 126.4, 111.7, 109.4, 77.7, 69.5, 38.7, 36.7, 30.6, 17.8 ppm.

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 magnesium sulfate (MgSO4)
  8. customThe solvent was removed under reduced pressure
  9. customthe remaining material was purified with column chromatography (EtOAc/n-hexane={fraction (1/7)})

Sources & evidence

ORD record
ord-bc71390c6c0b415d864e4b8b3393aa0a
Source dataset
uspto-grants-2005_03
Patent number
US06872840B1

Reaction notes

Loading…