Mechanistic Study on Selenium‐ and Sulfur‐Mediated Isomerization of Hydroxamic Acids

Abstract An in‐depth computational study reveals the intriguing mechanism of the recently reported isomerization of hydroxamic acids into para ‐aminophenols catalyzed by phenylselenyl bromide under mild conditions. The computations not only align with the reported experimental data, effectively explaining observed phenomena such as para ‐selectivity but also shed light on crucial aspects of the reaction mechanism that establish limitations on the scope of the studied rearrangement. Additionally, a joint theoretical/experimental study was performed to examine the potency of the phenylsulfenyl bromide to mediate the reaction under the same conditions.