Divergent Reactivity of Iminyl Radicals in Four Interrupted Pathways for the Synthesis of Cyclic/Acyclic Ketones and N-Heterocycles from Vinyl Azides and Phenylacetic Acids.

Herein, we report the Ag-catalyzed substrate-controlled interrupted radical pathways of the iminyl radical. The benzylic groups played a crucial role in pathway selection involving a series of dimerization and hydrolysis, a 1,5-H shift followed by cascade radical cyclization, and direct N-(sp2)/aromatization reactions that provide access to diverse cyclic/acyclic ketones, quinolines, and phenanthridine derivatives. Contrary to previous reports, mechanistic investigations with high-resolution mass spectrometry analysis uncovered the involvement of rare azine, oxime, and β-functionalized vinyl azide intermediates.