有机金属化合物的氟代反应
2020-01-17 08:39:45   来源:

格氏试剂,有机汞化合物,有机锡化合物等底物在一些亲电氟代试剂作用下,能转化为氟化合物。

其中格氏试剂的应用最多,也容易操作,缺点就是产率比较低。

反应实例

To a solution of4-chloro-5-bromo-7H-pyrrolo[2,3-d]pyrimidine (0.92 g, 4.0 mmol) in tetrahydrofuran (25mL) was added n-BuLi (2.5 Msolution in hexane, 3.48 mL) dropwise at –78 °C,and the reaction mixture was stirred at -78 °Cfor an additional 30 min.  To thissolution was added trimethylstannyl chloride (0.88 g, 4.4 mmol) in tetrahydrofuran (8 mL) dropwiseover a period of 10 min.  The reactionmixture was allowed to warm to room temperature and was stirred overnight.  Saturated aqueous ammonium chloride (60 mL)was added and extracted with ethyl acetate (3 ×70 mL).  The combined organic extracts were washedwith brine, dried over Na2SO4, and evaporated to dryness.  The residue was purified over silica gel togive the desired stannane (0.80 g,63%) as a colorless solid.

To a solution of this compound (1.97 g, 6.20 mmol) in acetonitrile (60mL) was added 1-(chloromethyl)- 4-fluoro-1,4- diazoniabicyclo[2.2.2]octanebis(tetrafluoroborate) (Selectfluor, 2.40 g, 6.5 mmol) in one portion, and the reaction mixture wasstirred at room temperature for 7 h.  Theprecipitate was filtered off, and the filtrate was evaporated in vacuo.  The residue was purified on silica gel usingethyl acetate/hexane (3:7) as the eluent to give the desired compound (0.22 g, 21%) as a colorless solid.

【 Eldrup, A. B. et al. J. Med. Chem. 2004, 47, 5284.】

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