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 (4-1) (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 (4-2) 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-a249cc4f4a3f44159580afdaa560d2b8

Source dataset

uspto-grants-2011_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07915252B2