Regioselective Ruthenium‐Catalyzed Carbonylative Direct Arylation of Five‐Membered and Condensed Heterocycles

A ruthenium‐catalyzed carbonylative C?H bond arylation process for the three‐component synthesis of complex aryl–(hetero)aryl ketones in an aqueous solution has been developed. By exploiting the ortho‐activating effect of nitrogen‐containing directing groups, a regioselective, successive twofold C(sp²)?C(sp²) bond formation has been achieved. This straightforward catalytic process provides access to versatile products prevalent in multiple bioactive compounds and supplies a valuable functional group for subsequent transformations.