Nickel-Catalyzed Addition of Arylboronic Acids to Alkyl Nitriles for Synthesis of Aryl Ketones in Fluorinated Solvent

Abstract

A mild and efficient nickel-catalyzed addition of arylboronic acids to alkyl nitriles in a fluorinated solvent for the synthesis of various aryl ketones is described. A broad range of arylboronic acids and alkyl nitriles were investigated, and the desired products were obtained with good to excellent yields under the optimized conditions. This method provides an opportunity for the synthesis of aryl ketones from alkyl nitriles, especially acetonitrile, with a non-noble metal catalyst in one pot.

Key words

nickel catalysis - arylboronic acids - alkyl nitriles - aryl ketones - fluorinated solvents

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• 15 1-[4-(Trifluoromethyl)phenyl]ethanone (3i); Typical Procedure The reaction was carried out in an autoclave containing a 10 mL Teflon reaction tube. The tube was charged with arylboronic acid 1i (1.0 mmol, 189.9 mg), MeCN (2; 1.0 mL), NaHCO₃ (2.0 equiv, 168.0 mg), H₂O (2.0 mmol, 36.0 mg), and a magnetic stirrer bar. NiBr₂·diglyme (17.6 mg, 5 mol%) and 1,10-phen (18.0 mg, 10 mol%) were then added to the tube, the autoclave was capped with a stopper and cooled with liquid N₂, and HCFC-244bb (2.0 mL, 2.6 g) was added by self-suction. The mixture was stirred at 100 °C for 5 h, then cooled to r.t. Excess HCFC-244bb was carefully vented, and H₂O (30 mL) was added to the mixture. The mixture was extracted with CH₂Cl₂ (3 × 15 mL), and the organic layers were combined, washed with brine, dried (Na₂SO₄), and concentrated under reduced pressure. The crude product was purified by column chromatography [silica gel, hexane–EtOAc (20:1)] to give a colorless oil; yield: 142.9 mg (76%). ¹H NMR (500 MHz, CDCl₃): δ = 8.09 (d, J = 8.0 Hz, 2 H), 7.76 (d, J = 8.5 Hz, 2 H), 2.68 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 197.1, 139.8, 134.5 (q, J_CF = 32.5 Hz), 128.7, 125.8 (q, J_CF = 3.8 Hz), 123.7 (q, J_CF = 271.1 Hz), 26.9. ¹⁹F NMR (470 MHz, CDCl₃): δ = –63.1 (s, 3 F).
• 16 1-(4-Hydroxyphenyl)heptan-1-one (3i) The reaction was carried as describe above with (4-hydroxyphenyl)boronic acid (1y; 1.0 mmol, 137.9 mg) and heptanenitrile (1.0 mL) to give a white solid; yield: 129.9 mg (63%); mp 62–63 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.91 (d, J = 8.5 Hz, 2 H), 6.91 (d, J = 9.0 Hz, 2 H), 6.67 (s, 1 H), 2.92 (t, J = 8.0 Hz, 2 H), 1.75–1.69 (m, 2 H), 1.40–1.35 (m, 2 H), 1.32–1.30 (m, 4 H), 0.88 (t, J = 7.0 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 200.3, 160.5, 130.8, 129.9, 115.4, 38.4, 31.7, 29.1, 24.8, 22.5, 14.0.