Synthesis of Symmetrical Biaryls through Palladium-Catalyzed Ligand-Free Homocoupling of Aryliodine(III) Diacetates

Abstract

An efficient process for the synthesis of symmetrical biaryls from readily available and bench-stable aryliodine(III) diacetates has been developed with high regional selectivity. The process exhibited high selectivities and good functional group tolerance with respect to methyl, bromo, chloro and cyano groups. Mechanistic studies revealed that the transformation involved in situ generation of aryl iodide from heating-promoted degradation of aryliodine(III) diacetate, followed by Ullmann-type homocoupling.

Key words

biaryls - palladium - homogeneous catalysis - coupling - chemoselectivity

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• 14 General Procedure (Preparation of 2): A mixture of aryliodine(III) diacetate 1 (0.2 mmol), K₂CO₃ (110.6 mg, 0.8 mmol, 4 equiv), Pd(OAc)₂ (4.5 mg, 0.02 mmol, 10 mol%) and DMF (2 mL) was stirred at 110 °C for 2 h. After cooling to r.t., the reaction mixtures were diluted with H₂O (10 mL) and filtered through a pad of silica gel that was then washed with Et₂O (3 × 10 mL). The combined organic phase was washed with brine (2 × 20 mL), dried over Na₂SO₄, filtered and concentrated in vacuo. The residue was then purified by flash chromatography on silica gel to provide the corresponding product. The product was characterized by GC–MS and NMR spectroscopy.