反应详情

To a degassed solution of methyl 4-(methyloxy)-2-{[(trifluoromethyl)sulfonyl]oxy}benzoate (77) (0.72 g, 2.30 mmol), Pd(PPh3)2Cl2 (0.16 g, 0.23 mmol), CuI (44 mg, 0.23 mmol), diisopropylethylamine (1.41 mL, 8.02 mmol) in DMF (10 mL) at room temperature was added 1-hexyne (0.55 mL, 4.60 mmol). The mixture was stirred at room temperature overnight. Poured into saturated aqueous NH4Cl (15 mL), the mixture was extracted with EtOAc. The combined organic extract was washed with water, brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as a dark brown oil. The crude product was purified by flash chromatography over SiO2 eluted with a gradient from hexanes to 5% EtOAc in hexanes to give 0.55 g (98%) of 78 as a light brown oil. 1H NMR (400 MHz, CDCl3): δ 0.95 (t, J=7.2 Hz, 3H), 1.45-1.58 (m, 2H), 1.60-1.70 (m, 2H), 2.48 (t, J=7.2 Hz, 2H), 3.83 (s, 3H), 3.87 (s, 3H), 6.82 (dd, J1=8.9 Hz, J2=2.6 Hz, 1H), 6.98 (d, J=2.5 Hz, 1H), 7.88 (d, J=8.8 Hz, 1H).

1. extractionthe mixture was extracted with EtOAc
2. extractionThe combined organic extract
3. washwas washed with water, brine
4. dry with materialdried over Na2SO4
5. filtrationfiltered
6. concentrationthe filtrate was concentrated
7. customto give the crude product as a dark brown oil
8. customThe crude product was purified by flash chromatography over SiO2
9. washeluted with a gradient from hexanes to 5% EtOAc in hexanes