Two‐Step, Telescopic Synthesis of Unsymmetrical Urea via Integration of Denitrogenative Methyl N ‐Arylcarbamates Formation and Their Aminolysis

Unsymmetrical ureas are valuable structural motifs in pharmaceuticals, agrochemicals, and functional materials; however, their synthesis often relies on toxic reagents, transition metals, or isocyanate intermediates, resulting in poor sustainability and limited scalability. Herein, we report an unconventional, transition metal‐free telescopic synthesis of unsymmetrical ureas through oxidative denitrogenative radical alkoxycarbonylation of amines using methyl carbazates, followed by direct base‐promoted aminolysis. Unlike previous carbamate‐based approaches that require isocyanate formation or are restricted to carbamate synthesis alone, this strategy enables seamless amine‐to‐urea conversion without intermediate isolation or isocyanate involvement. The protocol employs an inexpensive TBHP/I 2 system, exhibits broad substrate scope and excellent functional group tolerance, and is applicable to gram‐scale synthesis, pharmaceutical intermediates, and late‐stage drug functionalization. Mechanistic studies support a sequential radical denitrogenative coupling/nucleophilic substitution pathway, establishing the first telescopic application of denitrogenative chemistry of hydrazides for the construction of valuable urea frameworks.