Synthesis of Dibenzo[b,f]azepines via Palladium‐Catalyzed Cascade [4 + 3] Annulation of o‐Alkenyl Bromoarenes and o‐Bromoaniline Derivatives

Abstract A cascade [4+3] annulation of o ‐alkenyl bromoarenes and o ‐bromoaniline derivatives was described. Various dibenzo[ b , f ]azepines with substitutions on the 10/11 position were obtained in 14–97% yields. The synthetic versatility of this protocol is highlighted by the preparation of a precursor of the drug molecule oxcarbazepine, a gram‐scale synthesis, and two product transformations. Unlike previous amination/Heck sequence, this cascade process is supposed to undergo a C(vinyl), C(aryl)‐palladacycle involved pathway.