Advances in site-selective molecular editing have enabled structural modification on complex molecules. However, thus far, their applications have been restricted to C-H functionalization chemistry. The modification of the underlying molecular skeleton remains limited. Here, we describe a skeletal editing approach that provides access to benzazepine structures through direct nitrogen atom insertion into arenols. Using widely available arenols as benzazepine precursors, this alternative approach allowed the streamlined assembly of benzazepines with broad functional group tolerance. Experimental mechanistic studies support a reaction pathway involving dearomatizative azidation and then aryl migration. This study further highlights the potential for carbon-nitrogen transmutation sequences through combinations with oxidative carbon atom deletion, providing an alternative for the development of N-heteroarenes and demonstrating significant potential in materials chemistry.
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