反応 #74379

反応方程式

(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

溶媒

methanol

反応条件

後処理

1. 1
   温度After cooling to ambient temperature
2. 2
   workup.STIRRINGthe mixture was stirred at this temperature for 4 h
3. 3
   その他The solids were removed by filtration
4. 4
   洗浄the filter cake was washed with methanol
5. 5
   濃縮The combined filtrates were concentrated in vacuo
6. 6
   workup.DISSOLUTIONThe residue was dissolved in water (100 mL)
7. 7
   抽出extracted with a CHCl3/i-PrOH mixture (3/1, v/v, 5×100 mL)
8. 8
   乾燥The combined organic portions were dried over MgSO4 and conc. in vacuo
9. 9
   その他After triturating the residue with CH2Cl2 and EtOAc
10. 10
    ろ過the white solid was collected by filtration

実験手順

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.

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