Rhodium(III)-Catalyzed C-H bond Functionalization of 2-Pyridones with Alkynes: Switchable Alkenylation, Alkenylation/Directing Group Migration and Rollover Annulation.

Cp*Rh(III)-catalyzed chelation-assisted direct C-H bond functionalization of 1-(2-pyridyl)-2-pyridones with internal alkynes that can be controlled to give three different products in good yields has been realized. Depending on the reaction conditions, solvents and additives, the reaction pathway can be switched between alkenylation, alkenylation/directing group migration and rollover annulation. These reaction manifolds allow divergent access to a variety of valuable C6-alkenylated 1-(2-pyridyl)-2-pyridones, ( Z )-6-(1,2-diaryl-2-(pyridin-2-yl)vinyl)pyridin-2(1 H )-ones and 10 H -pyrido[1,2-a][1,8]naphthyridin-10-ones from the same starting materials. These protocols exhibit excellent regio- and stereo-selectivity, broad substrate scope, and good tolerance of functional groups. A combination of experimental and computational approaches have been employed to uncover the key mechanistic features of these reactions.