The Palladium‐catalyzed reaction of aromatic amides with maleimides results in the formation of a double C−H bond activation product, which occurs at both the benzylic and meta positions. Computational chemistry studies suggest that the first C−H bond activation unfolds via a six‐membered palladacycle, maleimide insertion, protonation of the Pd−N bond, and then activation of the meta C−H bond. The process concludes with reductive elimination, producing an annulation product. The energy decomposition analysis (EDA) showed that the deformation energy favors the ortho C‐H bond activation process. However, this route is non‐productive. The interaction energy controls the site where the maleimide is inserted into the Pd−C(sp3) bond, which determines its site selectivity. The energetic span model indicates that the meta C−H bond activation step is the one that determines the turnover frequency. Regarding the directing group, it has been concluded that the strong Pd‐S bonding and the destabilizing effect of the deformation energy allow the 2‐thiomethylphenyl to function effectively as a directing group.

The dehydrogenative coupling of aromatic amides with dimethyl itaconate proceeds smoothly under rhodium catalysis through ortho CÀ H bond cleavage directed by their amide group to produce benzylidenesuccinates. Aromatic carboxylic acids including benzoic and phthalic acids also [a] S.

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A rhodium(III)‐catalyzed redox‐neutral coupling of α‐trifluoromethylacrylic acid with bezamides proceeds smoothly accompanied by amide‐directed C−H bond cleavage to produce β‐[2‐(aminocarbonyl)phenyl]‐α‐trifluoromethylpropanoic acid derivatives. One of the products can be transformed to a trifluoromethyl substituted heterocyclic compound. In addition, the redox‐neutral coupling of α‐trifluoromethylacrylic acid with related aromatic substrates possessing a nitrogen‐containing directing group can also be conducted under similar conditions.

The oxidative coupling of benzamides with methyl 2trifluoromethylacrylate proceeds smoothly under rhodium(III) catalysis to produce trifluoromethyl-substituted isoindolinone derivatives. The catalyst system [Cp E RhCl 2 ] 2 /AgSbF 6 is effective for the oxidative coupling, while [Cp*RhCl 2 ] 2 /AgSbF 6 leads to their redox-neutral coupling predominantly. The oxidative coupling reactions with related acrylates have also been examined.