Compound C2

(Xantphos)Pd(CF2H)Cl

From: Controllable catalytic difluorocarbene transfer enables access to diversified fluoroalkylated arenes

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Compound data: Crystallographic data

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

To a 50 mL round flask bottle with a stir bar were added Pd[P(o-toyl)3]2 (730 mg, 1.0 mmol, 1.0 equiv) and anhydrous THF (20 mL) in glovebox. Difluoroacetic anhydride (210 μL, 1.5 mmol, 1.5 equiv) was then added dropwisely. After stirring for 30 min at room temperature, the resulting solution was filtered through a pad of Celite. The volatiles were removed under reduced pressure. The residue was dissolved in 50 mL benzene, and the resulting solution was heated to reflux for 1 h. After the reaction was cooled to room temperature, brine (50 mL) was added. The resulting mixture was stirred intensively for 3 h at room temperature. The organic layer was separated, dried over anhydrous Na2SO4, and filtered. The filtrate was concentrated under reduced pressure. The residue was dissolved in 20 mL CH2Cl2. Xantphos (578 mg, 1.0 mmol, 1.0 equiv) was then added to the solution. The resulting mixture was stirred for 30 min at room temperature. The reaction mixture was filtered through a pad of Celite. The filtrate was evaporated. The residue was dissolved in 50 mL methyl tert-butyl ether (MTBE) and kept at 4 oC for crystallization. The palladium complex was collected, washed with MTBE several times, and dried under vacuum to provide palladium complex C2 the as a yellow solid (656 mg, 85% yield). 1H NMR (400 MHz, CDCl3) δ 7.75 (br, 8 H), 7.57 (d, J = 7.0 Hz, 2 H), 7.45 – 7.32 (m, 12 H), 7.19 – 7.01 (m, 4 H), 5.65 (tt, J = 52.0 Hz, 16.0 Hz, 1 H), 1.76 (s, 6 H). 13C NMR (101 MHz, CDCl3) δ 154.73 (d, J = 5.6 Hz), 154.67 (d, J = 5.6 Hz), 134.53 (d, J = 6.9 Hz), 134.47 (d, J = 6.9 Hz), 133.89 (d, J = 2.2 Hz), 133.87 (d, J = 2.2 Hz), 131.86, 130.43, 130.28 (d, J = 21.6 Hz), 130.06 (d, J = 21.6 Hz), 128.54 (d, J = 5.1 Hz), 128.48 (d, J = 5.1 Hz), 127.65, 124.49 (d, J = 3.2 Hz), 124.45 (d, J = 3.2 Hz), 121.39 (d, J = 21.5 Hz), 121.17 (d, J = 21.5 Hz) 35.76, 29.22. (NOTE: The signal for carbon corresponding to Pd-CF2H is not shown in the spectrum). 19F NMR (376 MHz, CDCl3) δ -75.5 (q, J = 48.8 Hz, 2 F). 31P NMR (162 MHz, CDCl3) δ 9.4 (t, J = 48.8 Hz, 2 P). Sample for the X-ray crystal structure analysis was recrystallized from CHCl3/Hexane.