Synthesis of Aryl- and Alkylquinones through Rhodium-Catalyzed C–C ­Coupling under Mild Conditions

Abstract

A direct arylation, alkylation of quinones with aryl and alkyl boronic acids through rhodium-catalyzed C–C coupling has been developed under mild conditions. [Cp*RhCl₂]₂ was shown to be the most effective catalyst for the transformation. More importantly, good to excellent yields were obtained under room temperature and base-free conditions. This reaction provides a practical, efficient method for the synthesis of aryl- and alkylquinones.

Keywords

arylation - alkylation - quinones - rhodium - coupling

• References and Notes

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• 11 General Procedure for the Reaction of Benzoquinone with Boronic Acid To a solution of benzoquinone (0.5 mmol, 1.0 equiv) and [Cp*RhCl₂]₂ (0.025 mmol, 5 mol%) in CH₂Cl₂ (2 mL) was added the boronic acid (0.75 mmol, 1.5 equiv), H₂O (1 mL). Then the solution was stirred vigorously at r.t. for 10 h. Upon completion, the reaction was diluted with CH₂Cl₂ (3 mL) and washed with 5% NaHCO₃. The layers were separated, and the aqueous layer was extracted with CH₂Cl₂ (3 × 4 mL), dried over Na₂SO₄, and was evaporated to give the residue. The residue was then purified by column chromatography on silica gel (EtOAc–PE, 1:10) to provide the corresponding product 2-p-tolyl[1,4]benzoquinone (3b). ¹H NMR (400 MHz, CDCl₃): δ = 7.39 (d, J = 8.2 Hz, 2 H), 7.26 (d, J = 8.0 Hz, 2 H), 6.88–6.77 (m, 3 H), 2.40 (s, 3 H).