Aryl bromides containing a (1,4,5,6-tetrahydro-6-oxopyridin-3-yl)methyl substituent can be coupled with aryl halides yielding unsummetrical biaryls. In the course of this process, the cyclic enamide is oxidized to the 2(1H)-pyridinone. The reaction proceeds by a six-membered palladacycle resulting from allylic C-H bond activation of the cyclic enamide, leading to a six-membered palladacycle. A subsequent transmetalation reaction with an aryl-Pd-X intermediate eventually leads to mixed biaryls by reductive elimination and β-hydride elimination. The best yields were obtained with 2 equiv. of aryl halide. The required substrates were prepared from bromoiodobenzenes by a sequence consisting of a Heck reaction with allyl alcohol, enamine formation, Michael addition to ethyl acrylate, and heterocycle formation with benzylamine. © Wiley-VCH Verlag GmbH & Co. KGaA, 2008.