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Copper-Catalyzed Domino Halide Exchange-Cyanation of Aryl Bromides

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journal contribution
posted on 15.02.2003, 00:00 by Jacopo Zanon, Artis Klapars, Stephen L. Buchwald
An efficient copper-catalyzed domino halogen exchange-cyanation procedure for aryl bromides was developed utilizing 10 mol % CuI, 20 mol % KI, 1.0 equiv of the inexpensive N,N-dimethylethylenediamine as ligand, and 1.2 equiv of NaCN in toluene at 110 °C. The new method represents a significant improvement over the traditional Rosenmund−von Braun reaction:  the reaction conditions are much milder, and the use of stoichiometric amounts of copper(I) cyanide and polar solvents is avoided; therefore the isolation and purification of the aromatic nitrile products is greatly simplified. In addition, the new method exhibits excellent functional group compatibility comparable to that of the analogous Pd-catalyzed cyanation methodology.