Triethylamine → (E)-tert-butyl (2-(bromomethyl)-3-fluoroallyl)carbamate

To a stirring solution of (E)-tert-butyl 3-fluoro-2-(hydroxymethyl)-allylcarbamate (1.20 g, 5.85 mmol) in acetone (20 mL) at 0° C. under N2 was added sequentially triethylamine (1.22 mL, 8.77 mmol) and methanesulfonyl chloride (0.54 mL, 7.02 mmol). The resulting mixture was stirred at this temperature for 30 min. The reaction mixture was filtered to remove the precipitated salts and the filter cake was washed with further acetone (10 mL). The filtrate was charged with lithium bromide (2.54 g, 29.24 mmol) and the resulting suspension was stirred at room temperature for 1 h. The reaction mixture was partitioned between water (25 mL) and ethyl acetate (25 mL) and the aqueous layer was extracted with further ethyl acetate (25 mL). The combined organics were washed with brine (25 mL), dried over Na2SO4 and concentrated in vacuo to give (E)-tert-butyl 2-(bromomethyl)-3-fluoroallylcarbamate as a pale yellow oil (1.46 g, 93%). 1H-NMR (300 MHz; CDCl3) δ ppm: 1.47 (9H, s), 3.97 (2H, dd, J 3.5, 0.7 Hz), 4.02 (2H, br d, J 6.1 Hz), 4.78 (1H, br s), 6.79 (1H, d, J 81.1 Hz).

1. filtrationThe reaction mixture was filtered
2. customto remove the precipitated salts
3. washthe filter cake was washed with further acetone (10 mL)
4. stirringthe resulting suspension was stirred at room temperature for 1 h
5. customThe reaction mixture was partitioned between water (25 mL) and ethyl acetate (25 mL)
6. extractionthe aqueous layer was extracted with further ethyl acetate (25 mL)
7. washThe combined organics were washed with brine (25 mL)
8. dry with materialdried over Na2SO4
9. concentrationconcentrated in vacuo

ORD record

ord-185570a2d9924488870641e56a682072

Source dataset

uspto-grants-2016_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09302986B2