Rapid Ligand-Free Base-Accelerated Copper-Catalyzed Homocoupling Reaction of Arylboronic Acids

Abstract

A rapid, ligand-free, base-accelerated, copper-catalyzed homocoupling reaction of (het)arylboronic acids is presented. A ­CuCl₂·2H₂O/Na₂CO₃-based catalyst enabled the formation of bi(het)aryl compounds by a homocoupling process in moderate to excellent yields (72–97%) within 15 minutes. A mechanism for the copper-catalyzed base-accelerated reaction is proposed.

Key words

homocoupling - arylboronic acids - copper catalysis - biaryls

• References and Notes

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• 22 Bi(het)aryls 2a–t; General Procedure A vial was charged with the appropriate (het)arylboronic acid (0.3 mmol), CuCl₂·2H₂O (2.5 mg, 5 mol%), Na₂CO₃ (10 mol%), and MeOH (1 mL), and the mixture was stirred at 25 °C in the air for 5–15 min while the reaction was monitored by TLC. The reaction was then quenched with two drops of H₂O. The mixture was then diluted with EtOAc (2 mL) and filtered through a pad of MgSO₄ and silica. The pad was rinsed with additional EtOAc, and the solution was concentrated in vacuum. The crude material was purified by flash chromatography (silica gel). 4,4′-Di-tert-butylbiphenyl (2a) Prepared by following the general procedure with (4-tert-butylphenyl)boronic acid (53.4 mg, 0.3 mmol) for 15 min at r.t. Purification by flash chromatography (silica gel, PE) gave a white solid; yield: 37.9 mg (95%); mp 126–127 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.57 (d, J = 8.4 Hz, 4 H), 7.49 (d, J = 8.4 Hz, 4 H), 1.40 (s, 18 H). ¹³C{¹H} NMR (100 MHz, CDCl₃): δ = 149.9, 138.2, 126.6, 125.6, 34.5, 31.4.