反应详情

温度

0 °C

To a suspension of triphenyl(tetrahydro-2H-pyran-4-yl-methyl)phosphonium iodide (9.27 g) in THF (70 mL) was added dropwise lithium-1,1,1,3,3,3-hexamethyldisilazide (1 M THF solution, 19.0 mL) at 0° C. or lower, followed by stirring at around 0° C. for 1 hour. To the reaction mixture was added dropwise a solution of ethyl[3-bromo-4-(cyclopropylsulfanyl)phenyl](oxo)acetate (5.0 g) in THF (10 mL) at 2° C. or lower. The reaction mixture was stirred for 30 minutes under ice-cooling and then stirred at room temperature for 15 hours. 4 M Hydrochloric acid was added dropwise thereto at 10° C. or lower, adjusted to pH 7, and then concentrated under reduced pressure. To the residue was added diethyl ether and the resulting solid was separated by filtration. The filtrate was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain ethyl 2-[3-bromo-4-(cyclopropylsulfanyl)phenyl]-3-(tetrahydro-2H-pyran-4-yl)acrylate (4.57 g) as an (E)/(Z)-mixture of olefin.

1. additionwas added dropwise lithium-1,1,1,3,3,3-hexamethyldisilazide (1 M THF solution, 19.0 mL) at 0° C.
2. stirringThe reaction mixture was stirred for 30 minutes under ice-
3. temperaturecooling
4. stirringstirred at room temperature for 15 hours
5. customat 10° C.
6. concentrationconcentrated under reduced pressure
7. additionTo the residue was added diethyl ether
8. customthe resulting solid was separated by filtration
9. washThe filtrate was washed with water and saturated brine
10. dry with materialdried over anhydrous magnesium sulfate
11. concentrationconcentrated under reduced pressure
12. customThe residue was purified by silica gel column chromatography