Unlocking Electrophilic N-Aryl Intermediates from Aryl Azides, Nitroarenes, and Aryl Amines in Cyclization–Migration Reactions

Abstract An account of our development of reactions to construct N-heterocycles by triggering cyclization–migration tandem reactions from aryl azides, nitroarenes, and aryl amines is described. The reactivity patterns of metal N-aryl nitrenes, nitrosoarenes, N-aryl nitrogen radical anions, and N-aryl nitrenoids are compared. 1 Introduction 2 Unlocking the Reactivity Embedded in Aryl Azides 3 Exploiting the Reactivity of Nitrosoarenes Generated from Nitroarenes 4 Radical Anion N-Aryl Nitrogen Reactive Intermediates from Nitroarenes 5 Oxidation of Aryl Amines to Access Electrophilic N-Aryl Nitrenoids 6 Conclusion