Tris(furan-2-yl)phosphane → 2-Chloro-5-ethenyl-N-methylpyrimidin-4-amine

A mixture of (5-bromo-2-chloro-pyrimidin-4-yl)-methylamine (3.75 g, 16.9 mmol), tris(dibenzylidineacetone)dipalladium(0) (388 mg, 0.4 mmol), and tri-2-furylphosphine (777 mg, 3.3 mmol) in DMF is stirred for 20 minutes at room temperature and then tributylvinyltin (5.93 mL, 20.3 mmol) is added. After stirring for 16 hours at about 65° C., the reaction mixture is cooled to room temperature and stirred with a 10% aqueous solution of potassium fluoride (800 mL) and diethyl ether (600 mL) for 1 hour before filtering through a pad of Celite. The pad of Celite is rinsed with a further portion of diethyl ether (200 mL). The aqueous layer is separated and extracted with CHCl3. The combined organic extract is dried over MgSO4 and concentrated under reduced pressure to give crude oil which is purified by flash column chromatography (SiO2, EtOAc/Hx=1/4) to afford (2-chloro-5-vinyl-pyrimidin-4-yl)-methylamine (2.63 g, 92%) as a white solid.

1. stirringAfter stirring for 16 hours at about 65° C.
2. temperaturethe reaction mixture is cooled to room temperature
3. filtrationbefore filtering through a pad of Celite
4. washThe pad of Celite is rinsed with a further portion of diethyl ether (200 mL)
5. customThe aqueous layer is separated
6. extractionextracted with CHCl3
7. extractionThe combined organic extract
8. dry with materialis dried over MgSO4
9. concentrationconcentrated under reduced pressure
10. customto give crude oil which
11. customis purified by flash column chromatography (SiO2, EtOAc/Hx=1/4)

ORD record

ord-9453416f44ca43c193b96a4d2c1c0fdd

Source dataset

uspto-grants-2008_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07371750B2