反应详情

温度

-15 °C

Ref. Plietker, B. J. Org. Chem. 2004, 69, 8287-8296. In a 500 mL round-bottomed flask (t=g) was added sodium bicarbonate (827 mg, 9.84 mmol) with a stirring bar. Ruthenium(III) chloride (8.17 mg, 0.039 mmol) was added (aqueous solution was used in the ref but it was difficult to completely dissolve). To the solids was added water (3.94 mL), EtOAc (20 ml), and MeCN (20 ml) to afford a brown suspension. Oxone (1.21E+04 mg, 19.69 mmol) was added in one portion, resulting in the formation of a bright yellow suspension. The mixture was cooled to −20° C. (Z)-5-(2,3-difluorophenyl)cyclohept-1-ene (820 mg, 3.94 mmol) was added (with 7.2 ml 1/1 EtOAc/MeCN wash). The color instantly turned to slightly tan. The reaction was stirred at −20 ˜−15° C. for 1.5 hours. TLC showed no reaction. Warmed up to 0° C. for 10 minutes, but by TLC the reaction didn't improve much. It was warmed up to room temperature for 15-20 minutes. TLC showed disappearing of one major less polar spot (a minor one remained) and appearance of a more polar, slightly uv-active spot. The solids were filtered and washed with EtOAc. The organic solution was washed with aqueous NaHSO3 solution. The organic layer was dried with Na2SO4 and concentrated to a colorless oil. It was purified by FCC up to 5% MeOH/CH2Cl2. The more polar peak/peaks were pooled and concentrated to a colorless oil (169 mg, 18%). It was directly carried onto the next protection reaction.

1. dissolutionto completely dissolve)
2. customto afford a brown suspension
3. customresulting in the formation of a bright yellow suspension
4. additionwas added
5. wash(with 7.2 ml 1/1 EtOAc/MeCN wash)
6. customno reaction
7. temperatureWarmed up to 0° C. for 10 minutes
8. customby TLC the reaction
9. temperatureIt was warmed up to room temperature for 15-20 minutes
10. filtrationThe solids were filtered
11. washwashed with EtOAc
12. washThe organic solution was washed with aqueous NaHSO3 solution
13. dry with materialThe organic layer was dried with Na2SO4
14. concentrationconcentrated to a colorless oil
15. customIt was purified by FCC up to 5% MeOH/CH2Cl2
16. concentrationconcentrated to a colorless oil (169 mg, 18%)
17. customIt was directly carried onto the next protection reaction