Reacción #51140

Ecuación de reacción

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

potassium hexamethyldisilazide

→

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

Disolventes

EtOAc

THF

Condiciones de reacción

Tratamiento posterior

1. 1
   Temperaturacooled again to 0° C.
2. 2
   LavadoThe organic phase was washed with aqueous HCl (1 N), saturated aqueous sodium bicarbonate, and brine
3. 3
   Secadodried (Na2SO4)
4. 4
   Concentraciónconcentrated in vacuo
5. 5
   OtroThe resulting solid was purified by flash silica gel chromatography
6. 6
   Lavadoeluting with a gradient 0-4% EtOAc/hexanes

Procedimiento

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.

Fuente