Reacción #74379

Ecuación de reacción

(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

Disolventes

methanol

Condiciones de reacción

Tratamiento posterior

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

Procedimiento

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.

Fuente