Реакция #2122499

Уравнение реакции

8

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

diphenyl(trimethylsilyl)phosphine

pentane

→

compound

Выход 14.7%

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

Выход 14.7%

Растворители

toluene

Условия реакции

Обработка

1. 1
   Другоеevacuated
2. 2
   Другоеpurged with nitrogen three times
3. 3
   Температураcooled to room temperature
4. 4
   Другоеthe solvent evaporated under reduced pressure
5. 5
   ДругоеThe residue was chromatographed on a column of silica gel using first hexane
6. 6
   Другое9:1 hexane ethyl acetate as eluent to collect the product
7. 7
   ДругоеAfter evaporation of the solvent
8. 8
   workup.ADDITIONthe product 9 (10 g), a mixture of endo and exo isomers
9. 9
   Другоеwas obtained as white gummy material

Методика

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

Источник