반응 #336817

반응 방정식

8

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

diphenyl(trimethylsilyl)phosphine

pentane

→

compound

수율 14.7%

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

수율 14.7%

용매

toluene

반응 조건

후처리

1. 1
   기타evacuated
2. 2
   기타purged with nitrogen three times
3. 3
   온도cooled to room temperature
4. 4
   기타the solvent evaporated under reduced pressure
5. 5
   기타The residue was chromatographed on a column of silica gel using first hexane
6. 6
   기타9:1 hexane ethyl acetate as eluent to collect the product
7. 7
   기타After evaporation of the solvent
8. 8
   workup.ADDITIONthe product 9 (10 g), a mixture of endo and exo isomers
9. 9
   기타was obtained as white gummy material

실험 절차

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

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