High yield and selective electrocatalytic reduction of nitroarenes to anilines using redox mediators

Abstract

Anilines are major commodity chemicals used extensively in the production of pharmaceuticals, dyes, and polymers. However, the typical methods for synthesizing anilines suffer from poor environmental sustainability. Here, we report an electrocatalytic route for the production of anilines that works in aqueous solution at room temperature and pressure, where the electrons and protons required to reduce the nitrobenzene precursors are obtained from water. Excellent selectivities are obtained for a range of anilines, including species with ortho-iodides that are very challenging to obtain by other methods. Our approach relies on the use of a polyoxometalate redox mediator that shuts off the direct electro-reduction of the nitrobenzene at the electrode surface and thus prevents unproductive side reactions. Given the scale and current environmental impact of global aniline production, this electrochemical route holds promise for the development of more sustainable processes for the production of these vital chemical feedstocks. • Anilines are used extensively in the production of pharmaceuticals, dyes, and polymers • Current methods for the production of anilines are not environmentally sustainable • A more sustainable electrocatalytic redox-mediated route to anilines is reported • Reaction conditions are mild and selectivities for substituted anilines are high Anilines are major commodity chemicals that are usually produced via routes of questionable environmental sustainability. Stergiou and Symes report an electrocatalytic route to anilines that works in water at room temperature and pressure, holding promise for the development of more sustainable processes for the production of these vital chemical feedstocks.