The Azobis(isobutyronitrile)-Promoted\nOxidative Radical\nα‑Cyanation of Imine under Atmospheric O<sub>2</sub>

Herein, we report an azobis(isobutyronitrile) (AIBN)-promoted\nradical\nα-cyanation of <i>in situ</i> formed imine under atmospheric\nO<sub>2</sub>. This oxidative radical addition (ORA) procedure proceeds\nwith the sequential homocleavage of AIBN, extrusion of N<sub>2</sub>, and capture of O<sub>2</sub> toward an O-centered radical, which\nis converted to a cyano radical by β-scission. Then, the insertion\nof the cyano radical into the imine CN bond forms an aminyl\nradical, leading to α-cyano imine after 1,2-hydrogen atom transfer\n(HAT) and H abstraction. Such a transition-metal-free procedure features\nmild reaction conditions and a broad substrate scope, employing molecular\nO<sub>2</sub> as a clean terminal oxidant.