Triphenylphosphine → Diethyl (3,4,5-trifluorophenyl)phosphonate

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Trifluorobromobenzene (1.70 mL, 14.2 mmol), diethyl phosphite (2.20 mL, 17.1 mmol), N,N-dicyclohexylmethylamine (4.60 mL, 21.3 mmol) and ethanol (50 mL) were all combined in a nitrogen purged round bottom flask. After stirring for 5 minutes, triphenylphosphine (223 mg, 0.85 mmol) and palladium acetate (64 mg, 0.28 mmol) were added to the flask as one. The solution was heated to 76° C. and allowed to stir overnight. The solution started as a translucent brown color but was clearer by morning. Upon cooling, a silica plug (starting with hexanes as eluent, and increasing the polarity with ethyl acetate as needed) was run and a UV-active spot (Rf=0.35 in 1:1 hexanes:ethyl acetate) was isolated. The final product is a clear oil (3.477 g, 91% yield). 1H NMR (400.14 MHz, CDCl3) δ 7.44 (dt, J=14.4, 6.50 Hz 2H), 4.19-4.07 (m, 4H), 1.34 (t, J=7.07 Hz, 6H). 13C {1H} NMR (100.62 MHz, CDCl3) δ 151.1 (dddd, J=254.7, 25.4, 10.1, 2.9 Hz, 2C), 142.5 (dtd, J=258.6, 15.1, 3.3 Hz), 125.0 (dtd, J=194.5, 5.8, 5.2 Hz), 116.3-116 (m, 2C), 62.72 (d, J=5.63 Hz, 2C), 16.16 (d, J=6.34 Hz, 2C). 31P {1H} NMR (161.97 MHz, CDCl3): δ 14.94. Analysis calculated (found) %: C 44.79 (44.51), H 4.51(4.65). MS (FAB, m/z): 283 (M+, 100%). Exact mass calculated (found) for [M+H]+, m/z): 283.07109 (283.07135).

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