Breaking the Scalability Barrier: Diversifiable Pd-Catalyzed Domino Reaction En Route to Dibenzo[<i>b,d</i>]azepines

Herein, we present an efficient synthesis of diverse dibenzo[<i>b,d</i>]azepines in high yields via Pd-catalyzed domino reactions of 2,2’-dihalobiphenyls with <i>N</i>-allyl alkylamines. The key to this success is in situ generation of a five-membered, chelated Pd(IV) species via the subsequent activation of two C–Br bonds at the initial step, supported by control experiments, density functional theory, and machine learning calculations.