Homocoupling of Arylboronic Acids with a Catalyst System Consisting of a Palladium(II) N-Heterocyclic Carbene Complex and p-Benzoquinone

Abstract

In the presence of 1-3 mol% SIPr-ligated Pd(OAc)₂ and 0.6 equivalent of p-benzoquinone, various arylboronic acids underwent homocoupling in MeOH at ambient temperature to produce symmetrical biaryls in 38-96% yields.

Key words

biaryls - boron - catalysis - coupling - palladium

References and Notes

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17

Typical Procedure - Synthesis of 3a
To a solution of p-tolylboronic acid 2a (69.8 mg, 0.502 mmol) and p-benzoquinone (33.2 mg, 0.307 mmol) in MeOH (10 mL) was added 1a (3.25 mg, 0.0051 mmol), and the flask was evacuated and backfilled with Ar three times at -78 °C. The reaction mixture was stirred for 24 h at r.t. under Ar. The solvent was removed in vacuo and the residue was purified by silica gel column flash chromatography (eluent: hexane) to afford 3a (40.2 mg, 88%) as colorless solids. Other reactions were also carried out in a similar manner. If the product and excess pbq are inseparable by chromatog-raphy, crude materials were treated with excess NaBH₄ in MeOH at r.t. prior to purification. All starting materials and products are known compounds.