Regioselectivity was achieved in transition-metal-catalyzed arylation reactions via C–H bond cleavage through the use of chelation-assistance. Palladium, rhodium, and ruthenium complexes proved useful for the development of broadly applicable methodologies for intermolecular direct arylation reactions. These include protocols for direct arylation reactions using aryl chlorides and tosylates as well as transformations that proceed through the cleavage of unactivated C(sp³)–H bonds.