Twofold Electrochemical Amination of Naphthalene and Related Arenes

The twofold electrochemical amination reaction of polycyclic arenes, such as naphthalene (4), via Zincke intermediates is demonstrated for the first time. The installation of nitrogen functionalities occurs regioselectively in positions 1 and 5 of naphthalene (4). The key for this electroconversion is borondoped diamond as the anode material. The method of the multi-amination reaction is expanded to other aromatic substrates. A detailed study is provided, covering electrolysis parameters such as anode material, electrolyte system, current density, separator, and so forth. Despite the moderate yields, this approach offers the first direct electrosynthetic access to diaminated products.