Hemin-Catalyzed Oxidative Phenol-Hydrazone [3+3] Cycloaddition Enables Rapid Construction of 1,3,4-Oxadiazines

Abstract

Herein, we present a hemin-catalyzed oxidative phenol-hydrazone [3+3] cycloaddition that accommodates a broad spectrum of <i>N</i>-arylhydrazones, a class of less exploited 1,3-dipoles due to their significant Lewis basicity and weak tendency to undergo 1,2-prototropy to form azomethine imines. It renders expedient assembly of diversely functionalized 1,3,4-oxadiazines with excellent atom and step economy. Preliminary mechanistic studies point to the involvement of a one-electron oxidation pathway, which likely differs from the base-promoted aerobic oxidative scenario.