DFMBA試劑
N,N-二乙基-α,α-二氟-3-甲基芐胺有兩個容易消除的氟原子, Hara報道了用DFMBA在糖類和核苷類氟化羥基的高收率的得到相應的氟代化合物。

p-t-Butylbenzaldehyde (162 mg, 1 mmol), DFMBA (426mg, 2 mmol), and Et3N-3HF (161 mg, 1 mmol) were introduced into a reactor of a TeflonTM PFA tube with a diameter of 10 mm sealed atone end. The open end of the reactor was connected to a reflux condenser. Then, the reaction mixture was submitted for 20 min to microwave irradiation and during the irradiation, the temperature was kept at 180 oC. After cooling, the reaction mixture was poured into an aqueous NaHCO3 solution. The product was extracted with ether three times and the combined ethereal layers were dried over MgSO4. Purification by column chromatography (silica gel/hexane-ether) gave p-difluoromethyl-t-butylbenzene in 80% yield.
(Shingo Kobayashi, et al, Tetrahedron, 2004, 60, 6923–6930)
XtalFluor試劑
XtalFluor-E 和XtalFluor-M是由 Couturier和他的同事在2010年報道了它們的制備和應用,它們是固體的氟化試劑,比DAST,Deoxo-Fluor有著更好的穩定性。不像DAST,Deoxo-Fluor和FLUOLEAD在反應中會釋放出游離的氫氟酸,XtalFluor不會釋放出游離的氫氟酸,因此可以在普通的玻璃瓶中做反應,它比DAST有著更好的選擇性,同時能夠顯著減少消除的副產物。



To a solution of triethylamine trihydrofluoride (326 μL, 2.0 mmol) in dichloromethane(3.0 mL) at room temperature were successively added XtalFluor-E (344 mg, 1.5mmol) and 3-phenylpropionaldehyde (132 μL, 1.0 mmol). After 2 h, the reaction mixture was quenched at room temperature with a 5% aqueous sodium bicarbonate solution and stirred for 15 min, and the resulting mixture was extracted twice using dichloromethane. The organic phases were combined, dried over magnesium sulfate, and filtered through a pad of silica gel. Solvents were evaporated, and the resulting crude material was purified by silica gel flash chromatography using pentane to provide the title compound (119 mg, 76%) as a clear oil
示例:

To a solution of triethylamine trihydrofluoride (163 μL, 1.0 mmol) in 1,2-dichloroethane(2.0 mL) was added at room temperature XtalFluor-M (362 mg, 1.5 mmol) followed by 4-carbethoxycyclohexanone (159 μL, 1.0 mmol), and the reaction mixture was heated to reflux. After 2 h, the reaction mixture was cooled to room temperature, quenched with a 5% aqueous sodium bicarbonate solution, and stirred for 15 min,and the resulting mixture was extracted twice using dichloromethane. The organic phases were combined, dried over magnesium sulfate, and filtered through a pad of silica gel. Solvents were evaporated, and the resulting crude material was purified by silica gel flash chromatography using pentane to provide the title compound (166 mg, 86%) admixed with 4-carbethoxy-1-fluorocyclohex-1-ene(15:1 ratio respectively) as a clear oil
(L’Heureux,A. etal. J. Org. Chem. 2010, 75,3401)
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