Photocatalytic N–N Cross-Coupling to Access N ′-Aryl Hydrazides

For recent decades, hydrazides have been considered an attractive synthetic target due to their significant biological relevance. While conventional retrosynthetic procedures primarily rely on acyl substitution with premodified hydrazine nucleophiles, metal-nitrene-mediated approaches have recently emerged for N–N bond formation. Herein, we present a photoinduced, transition-metal-free coupling of both 1° and 2° aniline derivatives with 1,4,2-dioxazol-5-ones to afford N ′-aryl hydrazides, enabled by acridinium organophotocatalysts. Mechanistic studies led us to propose a sequential photocatalytic pathway involving: (i) oxidation of anilines to aminium radicals, (ii) PCET-mediated decarboxylative activation of dioxazolone leading to amidyl radical, and (iii) radical–radical coupling to afford the desired hydrazides.