反应详情

温度

70 °C

Trifluoro-methanesulfonic acid 11-allyl-8-oxo-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-trien-6-yl ester (600 mg, 1.60 mmol) was dissolved in methanol (4 mL) and DMSO (10 mL) under a N2 atmosphere and treated with triethylamine (356 g, 3.5 mmol), potassium acetate (16 mg, 0.16 mmol) and 1,3-bis(diphenylphosphine)propane (66 mg, 0.16 mmol). This mixture was stirred and degassed (3 vacuum/N2 purge cycles) and then treated with palladium acetate (36 mg, 0.16 mmol). The reaction vessel was flushed with carbon monoxide for 1 minute (bubbling through a needle) then placed under the balloon. After 10 min. the mixture was warmed to 70° C. for 2 h, cooled and poured into saturated aqueous NaCl solution (50 mL). The resulting mixture was extracted with EtOAc (4×25 mL) and the combined organic layer was washed with H2O (10 mL), saturated aqueous NaHCO3 solution (10 mL) and saturated aqueous NaCl solution (10 mL), dried over MgSO4, filtered, concentrated and purified by chromatography on silica gel eluting with 50% EtOAc/hexanes to provide an oil (260 mg, 57%). (TLC 50% EtOAc/hexanes Rf 0.30); 1H NMR (400 MHz, CDCl3) δ 7.46 (d, J=7.5 Hz, 1H), 7.28 (d, J=7.5 Hz, 1H), 7.23 (dd, J=7.5, 1.3 Hz, 1H), 5.47 (m, 1H), 4.93 (m, 2H), 3.91 (s, 3H), 3.16 (dd, J=8.9, 1.6 Hz, 1H), 3.11 (d, J=1.9 Hz, 1H), 2.80 (m, 3H), 2.65 (d, J=1.7 Hz, 1H), 2.45 (dd, J=11.0, 2.5 Hz, 1H), 2.31 (m, 2H), 1.88 (ddd, J=12.8, 5.5, 2.7 Hz, 1H); GCMS m/z 285 (M)+; IR (cm−1) 2941, 2786, 1732, 1685, 1286, 1146, 1142.

1. customdegassed
2. custom(3 vacuum/N2 purge cycles)
3. customThe reaction vessel was flushed with carbon monoxide for 1 minute (
4. custombubbling through a needle)
5. temperaturecooled
6. additionpoured into saturated aqueous NaCl solution (50 mL)
7. extractionThe resulting mixture was extracted with EtOAc (4×25 mL)
8. washthe combined organic layer was washed with H2O (10 mL), saturated aqueous NaHCO3 solution (10 mL) and saturated aqueous NaCl solution (10 mL)
9. dry with materialdried over MgSO4
10. filtrationfiltered
11. concentrationconcentrated
12. custompurified by chromatography on silica gel eluting with 50% EtOAc/hexanes