Reaction #2122499

Reaction equation

8

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

diphenyl(trimethylsilyl)phosphine

pentane

→

compound

Yield 14.7%

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

Yield 14.7%

Solvents

toluene

Conditions

Workup

1. 1
   Otherevacuated
2. 2
   Otherpurged with nitrogen three times
3. 3
   Temperaturecooled to room temperature
4. 4
   Otherthe solvent evaporated under reduced pressure
5. 5
   OtherThe residue was chromatographed on a column of silica gel using first hexane
6. 6
   Other9:1 hexane ethyl acetate as eluent to collect the product
7. 7
   OtherAfter evaporation of the solvent
8. 8
   workup.ADDITIONthe product 9 (10 g), a mixture of endo and exo isomers
9. 9
   Otherwas obtained as white gummy material

Procedure

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

Source