Tributylstannane → 4-Chloro-2-(tributylstannyl)pyrimidine

Temperatur

0 °C

To a solution of 1.5M (in cyclohexane) lithium diisopropylamide (mono THF) (9.06 mmol, 6.04 mL) in THF (15 mL) at 0° C. was added tri-n-butyltin hydride (2.34 g, 8.05 mmol) in THF (2 mL) dropwise. The reaction mixture was stirred at 0° C. for 15 minutes, then cooled to −78° C. To this solution was added 2,4-dichloropyrimidine (1 g, 6.71 mmol) in THF (7 mL) dropwise. The reaction mixture was stirred at −78° C. for 3 h, then warmed to 0° C. over 30 min. The reaction was quenched with saturated aqueous ammonium chloride (12 mL) at 0° C., then warmed to room temperature and extracted three times with ethyl acetate. The combined organic layers were dried over Na2SO4, filtered, and concentrated. Purification by flash column chromatography on silica gel (hexanes/DCM eluent) provided the product. LCMS-ESI+ calc'd for C16H30ClN2Sn (M+H+): 405.1; Found: 405.1 (M+H+). 1H NMR (400 MHz, CDCl3) δ 8.53 (dd, J=5.4, 1.3 Hz, 1H), 7.16 (dd, J=5.4, 1.2 Hz, 1H), 1.67-1.49 (m, 6H), 1.38-1.27 (m, 6H), 1.26-1.10 (m, 6H), 0.88 (td, J=7.5, 1.3 Hz, 9H).

1. temperaturecooled to −78° C
2. stirringThe reaction mixture was stirred at −78° C. for 3 h
3. temperaturewarmed to 0° C. over 30 min
4. customThe reaction was quenched with saturated aqueous ammonium chloride (12 mL) at 0° C.
5. temperaturewarmed to room temperature
6. extractionextracted three times with ethyl acetate
7. dry with materialThe combined organic layers were dried over Na2SO4
8. filtrationfiltered
9. concentrationconcentrated
10. customPurification by flash column chromatography on silica gel (hexanes/DCM eluent)
11. customprovided the product

ORD-Eintrag

ord-294e1b5104734641abcf2b06443f5e70

Quelldatensatz

uspto-grants-2015_03

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08987250B2