反应详情

温度

-60 °C

A 1-L 3-neck round-bottom flask was fitted with an addition funnel and the atmosphere was purged with nitrogen. Anhydrous, degassed THF (170 mL) was added to the 1-L flask and cooled to −60 ° C. (internal temperature). The addition funnel was charged with hexyllithium (2.38 M in hexanes, 57 mL, 135 mmol, 2.0 equiv). The hexyllithium was transferred into the cold THF over 20 min, maintaining the temperature below −40 ° C. The solution was re-cooled to −60 ° C. (internal temperature). A solution of 2′-iodo-2,4,6-triisopropylbiphenyl (27.5 g, 67.7 mmol, 1.0 equiv) in 170 mL of anhydrous, degassed THF was transferred, via cannula, drop wise to the n-hexyllithium solution. This was done over 25 min while maintaining the temperature below −40 ° C. After addition, the reaction mixture was allowed to stir at −60 ° C. for 30 min. Diethyl chlorophosphite (19.62 mL, 135 mmol, 2.0equiv) was added to the reaction mixture, over 10 min while maintaining the temperature below −40 ° C. After addition of diethyl chlorophosphite, the reaction was allowed to proceed at −60 ° C. for an additional 30 min. Aqueous hydrochloric acid (1 M, 338 mL, 338 mmol) was added at −60 ° C. The flask was removed from the cold bath and the reaction was allowed to warm to 22 ° C. The resultant solution was diluted with heptane (340 mL) and transferred to a separatory funnel. The layers were separated and the organic layer was assayed for product by quantitative HPLC (94% yield). The organic layer was concentrated under reduced pressure to give an oil which was used in the next reaction without further purification.

1. customA 1-L 3-neck round-bottom flask was fitted with an addition funnel
2. customthe atmosphere was purged with nitrogen
3. customAnhydrous, degassed THF (170 mL)
4. additionwas added to the 1-L flask
5. temperaturemaintaining the temperature below −40 ° C
6. temperatureThe solution was re-cooled to −60 ° C. (internal temperature)
7. temperaturewhile maintaining the temperature below −40 ° C
8. additionAfter addition
9. temperaturewhile maintaining the temperature below −40 ° C
10. waitto proceed at −60 ° C. for an additional 30 min
11. customThe flask was removed from the cold bath
12. temperatureto warm to 22 ° C
13. additionThe resultant solution was diluted with heptane (340 mL)
14. customtransferred to a separatory funnel
15. customThe layers were separated
16. concentrationThe organic layer was concentrated under reduced pressure
17. customto give an oil which
18. customwas used in the next reaction without further purification