反应详情

H2 is bubbled through a solution of 1 (280 mg, 1.54 mmol) and 10 mg of 10% Pd on carbon in 20 ml of MeOH for 1 hr. The catalyst is removed by filtration. Triethylamine (410 μl, 3.08 mmol) is added to the filtrate which was chilled on ice, then acryloyl chloride (250 μl, 3.08 mmol, Aldrich) in 10 ml of dry CH2Cl2 is added dropwise with stirring over 0.5 hr under Ar. The reaction is then allowed to return to ambient temperature, followed by 2 hr of stirring. Anion exchange resin (Bio-Rad, AG-MP1, OH−) (4 equivalents based on acryloyl chloride) is added, the mixture is filtered, and the filtrate is treated with sufficient cation exchange resin (Dowex, 50W×8, H+) to bring the mixture to neutrality (moist pH paper). The resin is removed by filtration, and the solvent is removed by rotary evaporation to yield an off-white solid (268 mg, 85%). ESI-MS (M+H)+: 206.1. 1H-NMR (acetone-d6) δ 9.15 (1H, br, NH), 7.78 (2H, d, J=9.0 Hz, NHCCH), 7.08 (2H, d, J=9.0 Hz, NHCCHCH), 6.55˜6.37 (2H, m, COCHCHH (anti to each other)), 5.75 (1H, dd, J=9.8 and 2.2 Hz, COCHCHH (syn to COCH)), 2.25 (3H, s, CH3).

1. customThe catalyst is removed by filtration
2. temperaturewas chilled on ice
3. customto return to ambient temperature
4. waitfollowed by 2 hr
5. stirringof stirring
6. additionAnion exchange resin (Bio-Rad, AG-MP1, OH−) (4 equivalents based on acryloyl chloride) is added
7. filtrationthe mixture is filtered
8. additionthe filtrate is treated with sufficient cation exchange resin (Dowex, 50W×8, H+)
9. customThe resin is removed by filtration
10. customthe solvent is removed by rotary evaporation