C([Li])CCCCC.I[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[C:15]1[C:20]([CH:21]([CH3:23])[CH3:22])=[CH:19][C:18]([CH:24]([CH3:26])[CH3:25])=[CH:17][C:16]=1[CH:27]([CH3:29])[CH3:28].[P:30](Cl)([O:34]CC)[O:31][CH2:32][CH3:33].Cl>C1COCC1>[CH:21]([C:20]1[CH:19]=[C:18]([CH:24]([CH3:25])[CH3:26])[CH:17]=[C:16]([CH:27]([CH3:29])[CH3:28])[C:15]=1[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=1[PH:30](=[O:34])[O:31][CH2:32][CH3:33])([CH3:22])[CH3:23]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, 2.0 equiv) 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.
불러오는 중…
