Potassium bis(trimethylsilyl)amide → Methyl 4-vinylbicyclo[2.2.2]octane-1-carboxylate

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.

1. temperaturecooled again to 0° C.
2. washThe organic phase was washed with aqueous HCl (1 N), saturated aqueous sodium bicarbonate, and brine
3. dry with materialdried (Na2SO4)
4. concentrationconcentrated in vacuo
5. customThe resulting solid was purified by flash silica gel chromatography
6. washeluting with a gradient 0-4% EtOAc/hexanes

ORD record

ord-25cc8f7fb801465897a61ea3c50f29e0

Source dataset

uspto-grants-2009_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07504402B2