Reaktion #601398

Reaktionsgleichung

caesium fluoride

2-(4-bromo-2,6-dichloro-phenyl)-3-methoxy-5-(2-pyridylmethyl)cyclopent-2-en-1-one

tributyl(prop-1-ynyl)stannane

N,N-dimethylformamide

caesium fluoride

tributyl(prop-1-ynyl)stannane

→

desired product

Ausbeute 32.1%

2-(2,6-dichloro-4-prop-1-ynyl-phenyl)-3-methoxy-5-(2-pyridylmethyl)cyclopent-2-en-1-one

Ausbeute 32.1%

Lösungsmittel

water

Et2O

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigesealed
2. 2
   Temperaturthe reaction heated at 120°C. under microwave irradiation for a further 30 minutes
3. 3
   Temperaturto cool to room temperature
4. 4
   Filtrationfiltered through Celite
5. 5
   SonstigeThe filtrate phases were separated
6. 6
   Extraktionthe aqueous phase extracted with further Et2O (2×10 ml)
7. 7
   WaschenThe combined organic extracts were washed with brine (10 ml)
8. 8
   Trocknendried over MgSO4
9. 9
   Filtrationfiltered
10. 10
    Sonstigeevaporated to dryness under reduced pressure
11. 11
    workup.DISSOLUTIONThe crude product was dissolved in EtOAc
12. 12
    Sonstigeabsorbed onto silica
13. 13
    Sonstigepurified by flash chromatography on silica using an EtOAc/isohexane gradient

Vorschrift

A microwave vial was charged with 2-(4-bromo-2,6-dichloro-phenyl)-3-methoxy-5-(2-pyridylmethyl)cyclopent-2-en-1-one (90 mg, 0.21 mmol), caesium fluoride (CsF, 64 mg, 0.42 mmol), copper(I) iodide (CuI, 8 mg, 0.042 mmol), dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (23 mg, 0.032 mmol), tributyl(prop-1-ynyl)stannane (83 mg, 0.25 mmol) and N,N-dimethylformamide (0.9 ml), sealed and heated at 120°C. under microwave irradiation for 30 minutes. Further caesium fluoride (32 mg, 0.21 mmol), copper(I) iodide (4 mg, 0.021 mmol), dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (12 mg, 0.016 mmol) and tributyl(prop-1-ynyl)stannane (42 mg, 0.13 mmol) were added and the reaction heated at 120°C. under microwave irradiation for a further 30 minutes. The reaction was allowed to cool to room temperature, diluted with water (10 ml) and Et2O (10 ml) and filtered through Celite. The filtrate phases were separated and the aqueous phase extracted with further Et2O (2×10 ml). The combined organic extracts were washed with brine (10 ml), dried over MgSO4, filtered and evaporated to dryness under reduced pressure. The crude product was dissolved in EtOAc, absorbed onto silica and purified by flash chromatography on silica using an EtOAc/isohexane gradient to give the desired product (26 mg, 32%). 1H NMR (400 MHz, CDCl3)δ ppm 8.50 (d, 1H), 7.60 (dd, 1H), 7.30 (2×s, 2×1H), 7.25 (d, 1H), 7.15 (dd, 1H), 3.75 (s, 3H), 3.40-3.35 (m, 1H), 3.20-3.10 (m, 1H), 3.00-2.90 (m, 1H), 2.85-2.80 (m, 2H), 2.05 (s, 3H).

Quelle