Electrocatalytic, Sm‐Promoted Synthesis of Aminoarenes from Nitroaromatic Derivatives in MeOH

A new mild and chemoselective method for the preparation of various aminoarenes is described, based on the electrochemical catalytic reduction of nitroaryl derivatives promoted by samarium salts in methanol. The reactions are carried out in air, in an undivided electrochemical cell, at room temperature and tolerate a wide range of functional groups, including some reducible ones, without leading to by‐products. This procedure is also effective for the complete reduction of challenging substrates, namely those capable of coordinating metals, traditionally leading to the need for drastic conditions in terms of pressure, reaction time or temperature. 47 examples are described, including one nitroalkane, and all lead to the targeted reduced product in yields that are almost always over 90%.