Electrochemically Driven Denitrative Cyanation of Nitroarenes.

A practical denitrative cyanation of feedstock nitroarenes under mild and transition metal-free reaction conditions has been developed. The key to success lies in the use of electrochemically driven, inexpensive ionic liquid -methylimidazolium -toluenesulfonate-promoted selective cathode reduction of nitroarenes to anilines, followed by diazoation, cathode reduction to form the aryl radical, and the essential radical cyanation process in one pot. Our protocol shows broad functional group tolerance and can be applied for the modification of bioactive targets.