C–H Homocoupling of Arenes via Pd/S,O‐Ligand Catalysis

Non‐directed Pd‐catalyzed oxidative dehydrogenative homocoupling of arenes is achieved in the presence of an S,O‐ligand. The reaction proceeds under aerobic and mild reaction conditions with a wide range of anisole derivatives, providing direct access to symmetric biaryls with excellent ortho ‐ ortho or para ‐ para regioselectivity. Notably, the use of the arene as the limiting reagent enables late‐stage functionalization of complex pharmaceutical molecules. The industrial applicability of this methodology is demonstrated through the synthesis of the Upilexmonomer via the homocoupling of unactivated o ‐xylene.