Beyond the Classic Approach: Iodine(lll/V) Reagents Mediated Hofmann Rearrangement for Construction of Nitrogen‐Containing Complex Molecules

Hypervalent iodine chemistry has revolutionized the Hofmann rearrangement by providing an environmentally benign alternative to traditional hazardous reagents. Employing compounds such as PhI(OAc) 2 and PhI(OCOCF 3 ) 2 , this strategy enables mild activation of amides to generate reactive isocyanate intermediates in situ. These intermediates readily engage with a range of nucleophiles including water, amines, alcohols, and carboxylic acids under mild conditions, facilitating the one‐pot synthesis of diverse nitrogen‐containing products. Unlike the classical Hofmann rearrangement, which affords only primary amines, this method allows efficient access to ureas, urethanes, carbamates, and amides. Key advantages include improved atom economy, simplified synthetic procedures, broad functional group tolerance, and enhanced applicability to complex molecule synthesis. This article highlights recent advances in hypervalent iodine‐mediated Hofmann rearrangements, offering a valuable resource for researchers developing novel routes to nitrogenous compounds in pharmaceutical and materials chemistry.