Palladium-Catalyzed CC Coupling of Aryl Halides with Isocyanides: An Alternative Method for the Stereoselective Synthesis of (3E)-(Imino)isoindolin-1-ones and (3E)-(Imino)thiaisoindoline 1,1-Dioxides

A palladium‐catalyzed, one‐pot cyclization reaction to construct (3E)‐(imino)isoindolin‐1‐ones and (3E)‐(imino)thiaisoindoline 1,1‐dioxides by introducing ortho‐reactive functional groups on aryl halides is reported. Under optimal conditions, the cyclization reaction afforded the corresponding products in good to excellent yields (up to 93%) with high stereoselectivity. Notably, this transformation successfully extends its application for the synthesis of phenanthridines and dibenzooxazepines. This new synthetic protocol not only extends the application platform for palladium‐catalyzed CC coupling of aryl halides with isocyanides, but also opens atom‐economic and step‐economic synthetic routes for nitrogen‐containing heterocyclic compounds with wide functional group compatibility.