Direct Amination of Aromatic C-H Bonds with Free Amines.

Aromatic amines belong to a highly important class of organic compounds which are found in various natural products, functional materials, and pharmaceutical agents. Their prevalence has sparked continuing interest in the development of highly efficient and environmentally benign synthetic strategies for the construction of these compounds. Cross-dehydrogenative coupling reactions between two unmodified C(X)-H bonds have recently emerged as a versatile and powerful strategy for the fabrication of new C(X)-C(X) bonds. In this context, several procedures have been reported for the synthesis of aromatic amines through the direct amination of aromatic C-H bonds with free amines. This review highlights recent advances and progress in this appealing research arena, with special emphasis on the mechanistic features of the reactions.