Dual Ligand Enabled Pd-Catalyzed <i>Ortho</i> -Alkylation of Iodoarenes

The synthesis of complex polysubstituted aromatic molecules from simple precursors is a central goal in organic chemistry. In this study, we developed an approach for the <i>ortho</i>-alkylation of iodoarenes utilizing a dual ligand catalytic system. By combining Pd/olefin ligand cooperative catalysis with bulky trialkylphosphine ligand-promoted C(sp²)-I reductive elimination, we have established an <i>ortho</i>-alkylative Catellani-type reaction with the aryl-iodine bond reconstruction as the final step, which opens new synthetic opportunities within the Catellani-type reactions. Through in-depth mechanistic investigations, we have isolated and characterized key organopalladium intermediates, revealing the synergistic interaction of the dual ligands in merging the Catellani-type process with C(sp²)-I reductive elimination. The present study showcases the unique advantages of Pd/olefin ligand catalysis and emphasizes the effectiveness of the dual ligand system in expanding the chemical space of the Catellani chemistry.