Palladium-Catalyzed Cyanation of Aryl Bromides with Malononitrile via ­Carbon–Nitrile Bond Cleavage Mediated by Copper

Abstract

An efficient palladium catalytic system is developed for the cyanation of aryl bromides using malononitrile as a cheap, less toxic, stable and easy-to-handle ‘nonmetallic’ cyanide source, which proceeds via copper-catalyzed cleavage of carbon–nitrile (C–CN) bonds. The approach provides a novel and alternative route leading to aryl nitriles.

Key words

aryl nitriles - cyanation - malononitrile - aryl bromides - palladium

• References and Notes

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• 10 Palladium-Catalyzed Cyanation, General Procedure A mixture of aryl bromide (0.250 mmol), malononitrile (0.500 mmol), Pd catalyst (0.005 mmol), CuI (0.125 mmol), 1,10-phenanthroline (0.063 mmol), t-BuONa (0.500 mmol) and KF (0.500 mmol) in DMF or NMP (1 mL) was stirred at 130 °C for 24 h. Upon completion of the reaction, the mixture was diluted with EtOAc (4.0 mL), and filtered through a bed of silica gel layered over Celite. The volatiles were removed in vacuo to afford the crude product. The extent of conversion was determined by GC. Further purification by column chromatography on silica gel afforded the desired product.All products are known compounds, which are identified by ¹H NMR, ¹³C NMR and MS, and compared with previously reported data.