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Abstract A Rh(I)‐catalyzed C6‐selective C−H arylation of 2‐pyridones with inexpensive, readily available, safe and structurally diverse aryl carboxylic acids with the aid of a pyridine directing group is developed. This decarbonylative arylation protocol features an easy‐to‐handle catalytic system, and is amenable to diversely substituted 2‐pyridones and aryl carboxylic acids. It allows access to a wide range of C6‐arylated 2‐pyridones, including those that are difficult to prepare using conventional C−H arylation processes. The method tolerates various electron‐neutral, electron‐rich and electron‐deficient functional groups, and affords the products in 41–91% yields. magnified imagemore » « less
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Xu, Xin; Luo, Chenguang; Zhao, Haoqiang; Pan, Yixiao; Zhang, Xin; Li, Jiajie; Xu, Lijin; Lei, Ming; Walsh, Patrick_J (, Chemistry – A European Journal)Abstract 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(1H)‐ones and 10H‐pyrido[1,2‐a][1,8]naphthyridin‐10‐ones from the same starting materials. These protocols exhibit excellent regio‐ and stereoselectivity, 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.more » « less
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