Phenyliodine(III) Diacetate (PIDA) Mediated Synthesis of Aromatic Azo Compounds through Oxidative Dehydrogenative Coupling of Anilines: Scope and Mechanism

An efficient and environmentally benign method has been developed for the synthesis of symmetrical and unsymmetrical aromatic azo compounds through phenyliodine(III) diacetate (PIDA) mediated oxidative dehydrogenative coupling of anilines in high yields. The scope of the reaction is broad for both homo‐ and cross‐dimerization. A plausible reaction mechanism has been proposed based on a structurally characterized key intermediate, suggesting that ethanol is involved in the reaction pathway. Fast reaction, metal‐free conditions, and functional‐group tolerance are advantages of this method.