反应详情

温度

0 °C

A three-necked round bottom flask was charged with the product from Example 6 (59.0 g, 0.182 mol) followed by CH2Cl2 (1.18 L). The resulting suspension was stirred briefly before adding allyltrimethylsilane (58 ml, 0.364 mol) all at once at room temperature. The suspension was cooled to 0° C. under nitrogen and was treated with BF3OEt2 (46.3 ml, 0.364 mol) dropwise keeping the reaction temperature below 2° C. After complete addition, the mixture was stirred at 0° C. for ˜1 hour. The completion of the reaction was monitored with HPLC until the starting material was consumed. The reaction mixture was poured into saturated NaHCO3 solution and stirred for 30 minutes. The organic layer was separated, washed with brine, dried over Na2SO4, treated with charcoal, filtered and concentrated to an oil. EtOH (200 ml) was added and the solution was concentrated to give a crystalline solid which was suspended with heptane at 0° C. for 2 hours before filtration to give a solid which was dried under reduced pressure at 45° C. to provide the title compound as a light yellow crystalline solid (60.1 g, 95.1%). Anal. Calcd for C23H25NO2: C, 79.51; H, 7.25; N, 4.03; Found: C, 79.26; H, 7.12; N, 3.80, 1H NMR [(CD3)2SO] δ1.16 (3H, s) 1.17 (3H, s), 2.18 (3H, s), 2.22 (1H, m), 2.46 (1H, m), 3.85 (3H, s), 5.01 (2H, m), 5.44 (1H, br s), 5.77 (1H, dd), 5.82 (1H, m), 6.10 (1H, br s), 6.52 (1H, d), 6.60 (1H, d), 6.70 (1H, d), 7.06 (1H, t,), 7.96 (1H, d); 13C NMR [(CD3)2SO] δ23.8, 28.8, 28.9, 36.5, 49.7, 55.6, 73.4, 105.6, 110.5, 113.4, 113.4, 116.1, 116.4, 127.3, 117.3, 127.3, 127.7, 132.2, 133.8, 134.5, 145.8, 151.1, 156.4. MS (APCI) m/z: 348 (M+H)+.

1. additionwas treated with BF3OEt2 (46.3 ml, 0.364 mol)
2. customthe reaction temperature below 2° C
3. additionAfter complete addition
4. stirringthe mixture was stirred at 0° C. for ˜1 hour
5. customwas consumed
6. additionThe reaction mixture was poured into saturated NaHCO3 solution
7. stirringstirred for 30 minutes
8. customThe organic layer was separated
9. washwashed with brine
10. dry with materialdried over Na2SO4
11. additiontreated with charcoal
12. filtrationfiltered
13. concentrationconcentrated to an oil
14. additionEtOH (200 ml) was added
15. concentrationthe solution was concentrated
16. customto give a crystalline solid which
17. filtrationwas suspended with heptane at 0° C. for 2 hours before filtration
18. customto give a solid which
19. customwas dried under reduced pressure at 45° C.