A Visible-Light-Induced α-Aminoalkyl-Radical-Mediated Halogen-Atom Transfer Process: Modular Synthesis of Phenanthridinone Alkaloids.

A halogen-atom transfer (XAT) strategy utilizing α-aminoalkyl radicals allows the generation of aryl radicals at room temperature, which is applied for intramolecular cyclization reactions en route to biologically relevant alkaloids. Starting from simple halogen-substituted benzamides under visible light irradiation in the presence of an organophotocatalyst (4CzIPN) and nBu3N allows the modular construction of the phenanthridinone core, which gives facile access to drug analogs and alkaloids, e.g., from the Amaryllidaceae family. The reaction pathway most likely involves a quantum mechanical tunneling enabled transfer event to achieve aromatization-halogen-atom transfer.