反応 #2122499

反応方程式

8

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

diphenyl(trimethylsilyl)phosphine

pentane

→

compound

収率 14.7%

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

収率 14.7%

溶媒

toluene

反応条件

後処理

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

実験手順

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

出典