Electrochemical Amination of Less-Activated Alkylated Arenes Using Boron-Doped Diamond Anodes

The anodic C–H amination of aromatic compounds is a powerful and versatile method for the synthesis of aniline derivatives. By using boron‐doped diamond (BDD) anodes, a method initially described by Yoshida et al. for electron‐rich arenes was expanded to less‐activated aromatic systems e.g., simple alkylated benzene derivatives. Anodes based on sp3 carbon seem to be the key for the electrochemical amination reaction. The corresponding primary anilines are obtained in good yields. Despite the cationic intermediates of the electrolytic reaction tert‐butyl moieties are tolerated. Diamond boosts the reactivity in the electrochemical amination reaction of less‐activated arenes as substrates. In 8 examples, alkylated arenes that are not converted at common carbon anodes are aminated at the aromatic core by using boron‐doped diamond (BDD) anodes. The corresponding anilines are obtained in a yield of up to 61 %.