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The 2-methoxyiminoacyl-mediated arylation of substituted phenylalanines has been examined. Selective monoarylation at the ortho position was achieved using pyridone ligands which decelerate the arylation process. Density functional theory (DFT) study of a continuous C-H arylation process that included the first and second arylation stage was performed. The computational result shows that the introduction of a pyridone ligand obviously disfavors the second arylation stage, which directly contributes to the selectivity between the mono/diarylated products. Furthermore, results of the kinetic isotope effect and a control experiment are agreed with DFT study.

The direct ortho‐alkynylation of substituted phenylalanine has been successfully achieved through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C−H functionalization. This innovative protocol showcases the ability to apply a diverse range of phenylalanine substrates, resulting in the efficient synthesis of alkynylation benzylamine derivatives with notable effectiveness. Computational investigations further revealed that the fluoride ion enhances the electropositivity of Pd(IV) and the interaction between C1 and C2 within the transition state of the reductive elimination, which significantly expedites the reductive elimination step in the alkynylation process. [ABSTRACT FROM AUTHOR]

The direct acetoxylation of substituted benzylamines has been accomplished through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C−H functionalization. A diverse array of phenylalanine substrates is amenable to this protocol, providing acetoxylation benzylamine derivatives with good to high efficiency. Computational results revealed that HOAc enhanced the stability of Pd−O bond, which obviously accelerate the reductive elimination step of the acetoxylation process. [ABSTRACT FROM AUTHOR]

[Display omitted] • Direct ortho -diarylation via MIA-mediated Pd-catalyzed C-H functionalization. • Di- ortho -arylated phenylalanine derivatives with good to high efficiency. • Localized orbital between Pd(IV) and Ag 2 CO 3 favored the reductive elimination step. The direct di -ortho -arylation of substituted phenylalanines has been accomplished via methoxyiminoacyl (MIA)-mediated Pd-catalyzed C H functionalization. A diverse array of phenylalanine substrates is amenable to this protocol, providing di -ortho -arylated phenylalanine derivatives with good to high efficiency. Computational results revealed that a bimetallic interaction between Pd(IV)-Ag(I) was formed through the localized orbital, which obviously favored the reductive elimination step of the arylation process. [ABSTRACT FROM AUTHOR]