Rh(III)-Catalyzed ortho-C–H amidation of ketones and aldehydes under cooperative metal organocatalysis has been utilized for synthesizing various ortho-amidocarbonyl analogs, and the reaction for the aldehyde proceeds at ambient temperature. The aniline derivative 3,5-bis(trifluoromethyl)aniline promotes the amidation reaction via a transient imine directing group. The efficient amidation agent is dioxazolone. The synthetic utility has been demonstrated in the synthesis of quindolinone alkaloids.