A highly efficient molecular iodine mediated formal [3 + 2 + 1] cycloaddition reaction for the direct synthesis of substituted quinolines from methyl ketones, arylamines, and styrenes is developed. The methyl group of the methyl ketone represents uniquely reactive input in the Povarov reaction. A self-sequenced iodination/Kornblum oxidation/Povarov/aromatization mechanism has been proposed as a possible reaction sequence ...