Noncovalent‐Interaction‐Dictated Product Selectivity in Intermolecular and Intramolecular Controllable Oxidation of Aromatic Amines Using 2,2′‐Diperoxyphenic Acid

Selective oxidation of aromatic amines is a valuable transformation in organic synthesis and medicinal chemistry as well as materials science. However, the efficient means to reach its full potential remain a formidable challenge because meticulous perturbations on the oxidation states can potentially lead to dramatically different product selectivity and efficacy profiles. Herein, by identifying bench‐stable and easily prepared 2,2′‐diperoxyphenic acid as oxidant and/or I 2 as additive, a general and divergent oxidation is developed to reliably form a wide assortment of nitrosobenzenes, nitrobenzenes, azobenzenes, and azoxybenzenes in an intermolecular and intramolecular controllable manner, avoiding the use of stoichiometric metal oxidants and transition metal‐based catalysts. Mechanistic studies reveal that the imposing of noncovalent interactions enables the achievement of reagent‐ and additive‐dependent reordering of NH bond reactivity and the rate of corresponding elementary steps.