Zr(OH)4‐Catalyzed Controllable Selective Oxidation of Anilines to Azoxybenzenes, Azobenzenes and Nitrosobenzenes

Abstract The selective oxidation of aniline to metastable and valuable azoxybenzene, azobenzene or nitrosobenzene has important practical significance in organic synthesis. However, uncontrollable selectivity and laborious synthesis of the expensive required catalysts severely hinders the uptake of these reactions in industrial settings. Herein, we have pioneered the discovery of Zr(OH) 4 as an efficient heterogeneous catalyst capable of the selective oxidation of aniline, using either peroxide or O 2 as oxidant, to selectively obtain various azoxybenzenes, symmetric/unsymmetric azobenzenes, as well as nitrosobenzenes, by simply regulating the reaction solvent, without the need for additives. Mechanistic experiments and DFT calculations demonstrate that the activation of H 2 O 2 and O 2 is primarily achieved by the bridging hydroxyl and terminal hydroxyl groups of Zr(OH) 4 , respectively. The present work provides an economical and environmentally friendly strategy for the selective oxidation of aniline in industrial applications.