反应 #2122499

反应方程式

8

5-[[(p-iodophenyl)oxy]methyl]bicyclo[2.2.1]hept-2-ene

diphenyl(trimethylsilyl)phosphine

pentane

→

compound

收率 14.7%

[p-(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)phenyl]diphenylphosphine

收率 14.7%

溶剂

toluene

反应条件

后处理

1. 1
   其他evacuated
2. 2
   其他purged with nitrogen three times
3. 3
   温度cooled to room temperature
4. 4
   其他the solvent evaporated under reduced pressure
5. 5
   其他The residue was chromatographed on a column of silica gel using first hexane
6. 6
   其他9:1 hexane ethyl acetate as eluent to collect the product
7. 7
   其他After evaporation of the solvent
8. 8
   workup.ADDITIONthe product 9 (10 g), a mixture of endo and exo isomers
9. 9
   其他was obtained as white gummy material

实验过程

Bis(acetonitrile)dichloropalladium(II) (1 mmol) was placed in a Schlenk flask, stoppered with a septum and evacuated and purged with nitrogen three times. To this flask was then added a solution of 8 (0.038 mol) in 100 mL of anhydrous toluene and 9.6 g of diphenyl(trimethylsilyl)phosphine. The resulting deep purple solution was heated at 70° C. overnight, then cooled to room temperature and the solvent evaporated under reduced pressure. The residue was chromatographed on a column of silica gel using first hexane and then 9:1 hexane ethyl acetate as eluent to collect the product. After evaporation of the solvent, the product 9 (10 g), a mixture of endo and exo isomers, was obtained as white gummy material. Addition of 50 mL of hot pentane to this compound resulted in the separation of white crystalline compound (2.1 g). 1H NMR (500 MHz, 25° C., CDCl3): δ (endo isomer, ˜85%) 7.30 (m, 12H, Ar—H), 6.88 (m, 2H, Ar—H), 6.18 (m, 1H, olefinic), 5.98 (m, 1H, olefinic), 3.72 (m, 1H, nor-CH2), 3.57 (m 1H, nor-CH2), 3.04 (br s 1H), 2.88 (br s, 1H), 2.53 (m, 1H), 1.92 (m, 1H), 1.51 (d, |J|=8.0 Hz), 1.32 (d, |J|=8.2 Hz, 1H), 0.65 (m, 1H); (exo isomer, partial) 6.92 (m, 2H, Ar—H), 4.05 (m, 1H), 3.88 (m, 1H). 31P {1H} NMR (200 MHz, 25° C., CDCl3): δ −6.57

来源