Synthesis of 2‐Aminoquinazolines through I2‐Catalyzed Cyclization of 2‐Aminoaryl Ketone Oximes and Isocyanides

An I2/cumene hydroperoxide (CHP)‐mediated tandem cyclization of 2‐aminoaryl ketone oximes with isocyanides has been developed. Various 2‐aminoquinazolines were obtained in 49‐96% yields under transition‐metal‐free conditions, and the resulting 4‐phenylquinazolin‐2‐amines show typical fluorescent emission properties. The key to the success of this strategy involves the formation of iminyl radical via the N‐O bond cleavage of hydroxy oxime.