Pd^II-catalyzed intermolecular amination of unactivated C(sp³)H bonds has been successfully developed for the first time. This method provides a new way to achieve the challenging intermolecular amination of unactivated C(sp³)H bonds, producing a variety of unnatural β²-amino carboxylic acid analogues. This C(sp³)H amination protocol is demonstrated with a broad substrate scope, good functional-group tolerance, and chemoselectivity. It is operated without use of phosphine ligand or external oxidant.

The first example of direct arylation of (di)azinyl aldoxime ethers by aryl iodides is reported. The reaction produces, in a single step, a variety of geometrically pure unsymmetrical (E)-(di)azinylaryl ketoxime ethers, a class of nitrogenated motifs that have found wide applications in medicinal and organic chemistry but are difficult to access using conventional procedure. The utility of the method is further illustrated in a formal synthesis of the Merck melanin-concentrating hormone 1 receptor antagonist.