반응 #51140

반응 방정식

methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate

potassium hexamethyldisilazide

→

methyl 4-vinylbicyclo[2.2.2]octane-1-carboxylate

용매

EtOAc

THF

반응 조건

후처리

1. 1
   온도cooled again to 0° C.
2. 2
   세척The organic phase was washed with aqueous HCl (1 N), saturated aqueous sodium bicarbonate, and brine
3. 3
   건조dried (Na2SO4)
4. 4
   농축concentrated in vacuo
5. 5
   기타The resulting solid was purified by flash silica gel chromatography
6. 6
   세척eluting with a gradient 0-4% EtOAc/hexanes

실험 절차

To a stirred solution of methyltriphenylphosphonium bromide (9.1 g, 12.8 mmol) in THF (50 ml) at 0° C. was added potassium hexamethyldisilazide (0.5M in toluene, 48.6 ml), dropwise over 5 min. The resulting mixture was allowed to warm up to room temperature over 1 h, then cooled again to 0° C. and treated with methyl 4-formylbicyclo[2.2.2]octane-1-carboxylate 15-A (Chapman, N. B. et al. J. Org. Chem., 1970, 35, 917) (2.5 g, 12.8 mmol). The reaction mixture was stirred at room temperature for 18 h then diluted with EtOAc (350 ml). The organic phase was washed with aqueous HCl (1 N), saturated aqueous sodium bicarbonate, and brine, then dried (Na2SO4) and concentrated in vacuo. The resulting solid was purified by flash silica gel chromatography, eluting with a gradient 0-4% EtOAc/hexanes. The resulting methyl 4-vinylbicyclo[2.2.2]octane-1-carboxylate 15-B was isolated as a clear, colorless oil.

출처