Compound 7

1-([1,1'-biphenyl]-4-yl)-2,2,3,3-tetrafluoropropan-1-one

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

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

General Procedure - Conditions D: To a 25 mL of Schlenk tube were added anhydrous K2CO3 (powder, 2.0 mmol, 4.0 equiv), hydroquinone (1.5 mmol, 3.0 equiv), PdCl2(PPh3)2 (7.5 mol%), Xantphos (20.0 mol%) and ArB(OH)2 (0.5 mmol, 1.0 equiv) under argon. BrCF2PO(OEt)2 (2.0 mmol, 4.0 equiv), H2O (0.5 mmol, 1.0 equiv) and fresh distilled 1,4-dioxane (5.0 mL) were added subsequently. The tube was screw-capped and heated to 80 oC (oil bath). After stirring for 18 h, the reaction was cooled to room temperature and fluorobenzene (1.0 equiv) was added. The yield was determined by 19F NMR before working up. The reaction mixture was then diluted with ethyl acetate, filtered through a pad of Celite® and concentrated. The residue after purification by silica gel chromatography to provide the desired product. Product 7 was prepared according to the conditions D outlined above on a 0.5 mmol scale. The product (99 mg, 70% yield) was obtained as a white solid (m.p. 55.8-57.2 oC) after purification by silica gel chromatography (EA : PE = 1 : 20). 1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 7.6 Hz, 2 H), 7.76 (d, J = 8.0 Hz, 2 H), 7.66 (d, J = 7.9 Hz, 2 H), 7.51 (t, J = 7.3 Hz, 2 H), 7.48 – 7.42 (m, 1 H), 6.33 (tm, J = 52.6 Hz, 1 H). 19F NMR (376 MHz, CDCl3) δ -118.6 (br, 2 F), -139.0 (dm, J = 52.6 Hz, 2 F). 13C NMR (126 MHz, CDCl3) δ 186.0 (t, J = 27.5 Hz), 148.0, 139.2, 130.7 (t, J = 3.2 Hz), 129.9 (t, J = 2.7 Hz), 129.1, 128.8, 127.5, 127.3, 110.4 (tt, J = 264.7 Hz, 26.9 Hz), 108.9 (tt, J = 250.8 Hz, 30.9 Hz). MS (EI): m/z (%) 282 (M+), 181 (100). HRMS: Calculated for C15H10OF4 (M+): 282.0668; Found: 282.0677.