Copper-Catalyzed Arylation of Arylboronic Acids with Aldehydes

Abstract

A novel copper-catalyzed arylation of arylboronic acids with aldehydes under oxygen atmosphere was achieved in the presence of Cu(OTf)₂ and Xantphos, affording diaryl ketone derivatives in moderate to good yields. The efficiency of this reaction was demonstrated by the compatibility with fluoro, bromo, chloro, nitro, ­methylsulfonyl, and trifluoromethyl groups.

Key words

arylation - diaryl ketones - copper - catalysis

References and Notes

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22

General Procedure for the Synthesis of Diaryl Ketones Under nitrogen atmosphere, a Schlenk tube was charged with aldehyde (0.3 mmol), arylboronic acid (0.6 mmol), Cu(OTf)₂ (10 mol%), Xantphos ligand (15 mol%), and KF˙2H₂O (0.6 mmol) in toluene (2 mL) under ice-salt
(-20 ˚C). The mixture was stirred for 6 h at r.t. under nitrogen atmosphere. Then pass into the oxygen, the mixture was stirred for 0.5 h at r.t. and heated up to reflux temperature (about 120 ˚C) for 24 h under oxygen atmosphere. After the completion of the reaction, as monitored by TLC, the solvent was concentrated in vacuo, and the residue was purified by flash column chromatog-raphy on silica gel (300-400 mesh) with PE-EtOAc as eluent to give the desired product.
Naphthalen-2-yl(4-nitrophenyl)methanone (3ai, Table 3, Entry 9)
^¹H NMR (300 MHz, CDCl₃): δ = 7.57-7.69 (m, 2 H), 7.91-8.00 (m, 6 H), 8.23 (s, 1 H), 8.22-8.40 (m, 2 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 123.6, 125.2, 127.2, 127.9, 128.8, 129.0, 129.5, 130.7, 132.1, 132.4, 133.5, 135.6, 143.2, 149.8, 194.8. ESI-MS: m/z (%) = 278 (100) [M + 1]⁺. Anal. Calcd for C₁₇H₁₁NO₃: C, 73.64; H, 4.00. Found: C, 73.66; H, 4.05.
4-Methylsulfonylphenyl(4-tolyl)methanone (3db, Table 3, Entry 12)
^¹H NMR (300 MHz, CDCl₃): δ = (s, 3 H), 3.12 (s, 3 H), 7.32 (d, J = 8.1 Hz, 2 H), 7.71 (d, J = 8.1 Hz, 2 H), 7.93 (d, J = 8.4 Hz, 2 H), 8.06 (d, J = 8.4 Hz, 2 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 21.7, 44.4, 127.4, 129.3, 130.3, 133.7, 142.7, 143.2, 144.5, 194.8. ESI-MS: m/z (%) = 275 (100) [M + 1]⁺. Anal. Calcd for C₁₅H₁₄O₃S: C, 65.67; H, 5.14. Found: C, 65.82; H, 5.22.
2,6-Dinitrophenyl(4-tolyl)methanone (3hb, Table 3, Entry 16)
^¹H NMR (300 MHz, CDCl₃): δ = (s, 3 H), 7.29 (d, J = 8.1 Hz, 2 H), 7.63 (d, J = 8.1 Hz, 2 H), 7.70 (d, J = 8.1 Hz, 2 H), 8.62 (d, J = 8.1 Hz, 2 H), 9.08 (s, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 21.8, 120.1, 128.4, 129.6, 129.8, 130.3, 132.4, 141.7, 146.0, 146.0, 148.4, 190.9. MS (EI): m/z (%) = 287 (100) [M + 1]⁺. Anal. Calcd for C₁₄H₁₀N₂O₅: C, 58.74; H, 3.52. Found: C, 58.83; H, 3.63.