Direct Conversion of Amines to Organic Azides Under Nitrite‐Free Conditions Enabled by In Situ Nitrous Acid Formation

We present a unified and operationally straightforward strategy for the direct synthesis of azide and aryltriazole derivatives under nitrite‐free conditions. This dual catalytic platform encompasses two mechanistically distinct pathways: (i) a potassium iodide‐catalyzed protocol involving the in situ generation of nitrous acid from hydroxylamine hydrochloride and tert‐ butyl hydroperoxide, mediated by catalytically generated iodine (I 2 ), which facilitates the diazotization of primary amines followed by NN bond formation to furnish azide motifs; and (ii) an iron(III)‐catalyzed transformation that bypasses conventional diazonium intermediates, promoting intramolecular cyclization of hydroxylamine‐derived species to access aryltriazoles. Both approaches obviate the need for traditional nitrite salts or preformed azide reagents, offering a metal‐efficient and environmentally benign alternative. The methodology demonstrates broad substrate scope across aromatic and aliphatic amines, affording structurally diverse nitrogen‐rich products in yields of up to 93%. By eliminating reliance on hazardous nitrite‐based reagents, this work provides a sustainable and versatile platform for the synthesis of valuable azide‐containing scaffolds with broad synthetic applicability.