反应详情

An oven-dried Schlenk tube was cooled to room temperature under an argon purge, and was charged with magnesium turnings (54 mg, 2.2 mmol), THF (2 mL), and 1,2-dibromoethane (9 μL). The mixture was stirred at room temperature for 15 min, then a solution of 2 (618 mg, 2.0 mmol) in 1 mL THF was added dropwise. The mixture was stirred at rt for 1 h, then the septum was removed from the flask, and copper (I) chloride (283 mg, 2.1 mmol) was added. The tube was capped with the septum and purged with argon for 1 min. The tube was charged with di-t-butylchlorophosphine (0.46 mL, 2.4 mmol) and additional THF (1 mL). The mixture was heated to 60° C. with stirring for 26 h. The mixture was cooled to room temperature and filtered, and the solids were washed with ether/hexanes (50 mL, 1/1 v/v). The organic solution was poured into a separatory funnel and washed with ammonium hydroxide solution (3×50 mL), and brine (50 mL). The organic phase was then dried over anhydrous sodium sulfate, filtered, and concentrated. The crude material was recrystallized from hot methanol to afford 191 mg (26%) of 3 as a white, crystalline solid.

1. custompurge
2. stirringThe mixture was stirred at rt for 1 h
3. additionwas added
4. customThe tube was capped with the septum
5. custompurged with argon for 1 min
6. temperatureThe mixture was heated to 60° C.
7. stirringwith stirring for 26 h
8. temperatureThe mixture was cooled to room temperature
9. filtrationfiltered
10. washthe solids were washed with ether/hexanes (50 mL, 1/1 v/v)
11. additionThe organic solution was poured into a separatory funnel
12. washwashed with ammonium hydroxide solution (3×50 mL), and brine (50 mL)
13. dry with materialThe organic phase was then dried over anhydrous sodium sulfate
14. filtrationfiltered
15. concentrationconcentrated
16. customThe crude material was recrystallized from hot methanol