反应详情

温度

-78 °C

Compound 2 (37 g, 0.079 mol) was dissolved in 200 mL of anhydrous THF and cooled to −78° C. To this solution was added n-BuLi (2.5 M in hexane, 94 mL, 0.24 mol) slowly to maintain the temperature below −60° C. After addition, the orange-yellow solution was stirred at −78° C. for an hour. Compound 1 (60.2 g, 0.24 mol) was dissolved in 100 mL of anhydrous THF and added dropwise to the above cooled solution. The reaction was slowly warmed up to room temperature and stirred at room temperature overnight. The reaction was quenched with HI aqueous solution (47% in water, 143 mL, 0.79 mol) and TBDMS group was also de-protected. The deep brown reaction was heated to reflux for 10 min. and most of the solvent was removed under reduced pressure. The reaction mixture was then extracted with methylene chloride three times. The combined organic phase was washed with saturated sodium metabisulfate solution, water, and brine, and dried over MgSO4. The crude product was obtained as brown viscous oil and was purified by column chromatography on silica gel with 10/90 ether/hexane as an eluent. The pure product was obtained as 22.4 g light yellow brown solid at 51% yield. 1H NMR (CDCl3) δ (ppm): 0.91 (t, J=7.0 Hz, 6H), 1.26-1.43 (m, 8H), 1.71-1.81 (m, 2H), 2.73 (t, J=7.8 Hz, 2H), 5.21 (s, br, 2H, OH), 6.89 (d, J=2.3 Hz, 2H), 6.96 (dd, J1=9.5 Hz, J2=2.5 Hz, 2H), 7.32 (d, J=8.6 Hz, 4H, phenyl), 7.35 (d, J=8.6 Hz, 4H, phenyl), 7.57 (d, J=9.4 Hz, 2H). 13C NMR (CDCl3): 14.16, 22.72, 29.26, 29.52, 31.60, 31.86, 35.90, 106.84, 118.58, 127.07, 128.46, 128.98, 129.64, 131.04, 134.94, 136.30, 142.10, 151.69. Mp 162-164° C. FD-MS: m/z 558 (M+).

1. temperatureto maintain the temperature below −60° C
2. additionAfter addition
3. additionadded dropwise to the above cooled solution
4. temperatureThe reaction was slowly warmed up to room temperature
5. stirringstirred at room temperature overnight
6. customThe deep brown reaction
7. temperaturewas heated
8. temperatureto reflux for 10 min. and most of the solvent
9. customwas removed under reduced pressure
10. extractionThe reaction mixture was then extracted with methylene chloride three times
11. washThe combined organic phase was washed with saturated sodium metabisulfate solution, water, and brine
12. dry with materialdried over MgSO4
13. customThe crude product was obtained as brown viscous oil
14. customwas purified by column chromatography on silica gel with 10/90 ether/hexane as an eluent