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 I₂ 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 NH bond reactivity and the rate of corresponding elementary steps.