Abstract 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.

Abstract The transformation of cyclobutanones into acyclic carbonyl compounds through a Pd-catalyzed C–C bond cleavage is reported. The use of an N-heterocyclic carbene ligand efficiently promoted the ring opening and functionalization of various cyclobutanones, not only with alcohols, but also with N-centered nucleophiles, such as aniline or amide derivatives. Cyclobutanones were also found to react with arylboronic esters, resulting in the production of acyclic aryl ketones.

Nucleophilic aromatic substitution (S_NAr) reactions of non-activated aryl fluorides with amide enolates are reported. DFT calculations suggest that the reaction proceeds through a concerted S_NAr pathway.

A palladium-catalyzed reaction of N-phthaloyl hydrazones derived from aldehydes and cyclobutanones, leading to the production of nitriles, is described.

The first Pd-catalyzed 1,1-alkynylbromination of terminal alkenes using alkynyl bromides, which provides direct access to a variety of functionalized propargylic bromides without the need for an external brominating reagent, is reported.

Axially chiral biaryl units are key components of natural products and biologically active compounds as well as chiral molecular catalysts, and thus significant efforts have been focused on the efficient synthesis of atropisomerically enriched axially chiral biaryls. Among a variety of strategies, dynamic kinetic resolution is considered as an efficient method in asymmetric synthesis since highly enantio-enriched products could be furnished in quantitative yields from racemic starting materials in the best case. This review highlights recent progress of dynamic kinetic asymmetric transformations of racemic axially chiral biaryls by using transition-metal catalysts.