Free-Amine Directed Arylation of Biaryl-2-amines with Aryl Iodides by Palladium Catalysis

A new palladium-catalyzed free-amine directed arylation of C(sp²)–H bonds in the presence of AgOAc and TFA is described. Biaryl-2-amines react with various aryl iodides to give the corresponding mono- or diarylated products with exclusive regioselectivity

Copper-Catalyzed Reaction of Ketenimine and in Situ Generated Immonium Ion: Access to α<i>,</i>β‑Unsaturated Amidines

A Cu-catalyzed three-component reaction of alkyne, azides (sulfonyl or phosphoryl azides), and <i><i>N</i></i>,<i><i>N</i></i>-dialkyloxyformamide dialkyl acetal via electrophilic addition of immonium ion to copper ketenimine is reported. This new protocol for the preparation of α,β-unsaturated amidine derivatives appears to offer high yield, mild conditions, and wide substrate scope. The reaction might involve the processes of copper ketenimine intermediate formation, electrophilic addition, and isomerization

Cu(II)-Promoted Palladium-Catalyzed C–H Ortho-Arylation of <i>N</i>,<i>N</i>‑Dimethylbenzylamines

A novel protocol for palladium-catalyzed arylation of the C­(sp²)–H bond directed by a <i>N</i>,<i>N</i>-dimethylaminomethyl group in the presence of AgOAc and Cu­(OAc)₂·H₂O is described. Various aryl iodides proved to be efficient coupling partners, furnishing the corresponding ortho monoarylated or diarylated arenes in moderate to good yields. Cu­(OAc)₂·H₂O is found to be the important additive to improve the yields in this transformation