Rosenmund Reaction

Aryl nitriles can be prepared by the cyanation of aryl halides with an excess of copper(I) cyanide in a polar high-boiling solvent such as DMF, nitrobenzene, or pyridine at reflux temperature.

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Mechanism of the RoseMUND Reaction

The mechanism probably involves the formation of a Cu(III) species through oxidative addition of the aryl halide. Subsequent reductive elimination then leads to the product:

The excess of copper cyanide and the use of a polar, high-boiling point solvent makes the purification of the products difficult. In addition, elevated temperatures (up to 200°C) lower the functional group tolerance. The use of alkali metal cyanides or cyanation reagents such as cyanohydrins, a catalytic amount of copper(I) iodide and kalium iodide, allows a mild, catalytic cyanation of various aryl bromides.

If aryl iodides, sodium cyanide and copper(I) iodide are used, a simple mechanism similar to that of an Ullmann-type reaction can be proposed:

Reactions with aryl bromides and added alkali metal iodides involve additional equilibria in which aryl bromides give the more reactive aryl iodides:

Recent Literature

Copper-Catalyzed Domino Halide Exchange-Cyanation of Aryl Bromides