Réaction #74379

Équation de réaction

(1R,2S,4R,5S)-2,5-bis(trimethoxysilyl)bicyclo[2.2.1]heptane

potassium hydrogen fluoride

tetrahydrofuran

urea hydrogen peroxide

→

desired product

(1R,2S,4R,5S)-Bicyclo[2.2.1]heptane-2,5-diol

Solvants

methanol

Conditions de réaction

Traitement

1. 1
   TempératureAfter cooling to ambient temperature
2. 2
   workup.STIRRINGthe mixture was stirred at this temperature for 4 h
3. 3
   AutreThe solids were removed by filtration
4. 4
   Lavagethe filter cake was washed with methanol
5. 5
   ConcentrationThe combined filtrates were concentrated in vacuo
6. 6
   workup.DISSOLUTIONThe residue was dissolved in water (100 mL)
7. 7
   Extractionextracted with a CHCl3/i-PrOH mixture (3/1, v/v, 5×100 mL)
8. 8
   SéchageThe combined organic portions were dried over MgSO4 and conc. in vacuo
9. 9
   AutreAfter triturating the residue with CH2Cl2 and EtOAc
10. 10
    Filtrationthe white solid was collected by filtration

Mode opératoire

To (1R,2S,4R,5S)-2,5-bis(trimethoxysilyl)bicyclo[2.2.1]heptane (76.9 mmol) was added potassium hydrogen fluoride (33.0 g, 423 mmol), tetrahydrofuran (80.0 mL), methanol (80.0 mL), and urea hydrogen peroxide addition compound (65.0 g, 691 mmol, Aldrich). The resulting white slurry was stirred overnight at 60° C. After cooling to ambient temperature, MnO2 (0.56 g, 6.4 mmol) was added, and the mixture was stirred at this temperature for 4 h. The solids were removed by filtration, and the filter cake was washed with methanol. The combined filtrates were concentrated in vacuo. The residue was dissolved in water (100 mL) and extracted with a CHCl3/i-PrOH mixture (3/1, v/v, 5×100 mL). The combined organic portions were dried over MgSO4 and conc. in vacuo. After triturating the residue with CH2Cl2 and EtOAc, the white solid was collected by filtration. This material was the title compound. A second crop of desired product was obtained by flash column chromatography (0-5% MeOH in EtOAc) from the concentrated filtrate.

Source