Triethylamine → 11-Allyl-8-oxo-11-aza-tricyclo[7.3.1.02,7]trideca-2(7),3,5-triene-6-carboxylic acid methyl ester

Participants

Reaction Conditions

Reaction Steps

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.

Provenance & Evidence