Sequential Cross‐Coupling/Annulation of ortho‐Vinyl Bromobenzenes with Aromatic Bromides for the Synthesis of Polycyclic Aromatic Compounds

: A sequential cross-coupling/annulation of ortho-vinyl bromobenzenes with aromatic bromides was realized, providing a direct and modular approach to access polycyclic aromatic compounds. A vinyl-coordinated palladacycle was proposed as the key intermediate for this sequential process. Excellent chemoselectivity and regioselectivity were observed in this transformation. The practicability of this method is highlighted by its broad substrate scope, excellent functional group tolerance, and rich transformations associated with the obtained products.