Recent Advances in Transition-Metal-Catalyzed, Directed Aryl C–H/N–H Cross-Coupling Reactions

Amination and amidation of aryl compounds using a transition-metal-catalyzed cross-coupling reaction typically involves prefunctionalization or preoxidation of either partner. In recent years, a new class of transition-metal-catalyzed cross-dehydrogenative coupling reaction has been developed for the direct formation of aryl C–N bonds. This short review highlights the substantial progress made for ortho -C–N bond formation via transition-metal-catalyzed chelation-directed aryl C–H activation and gives an overview of the challenges that remain for directed meta - and para -selective reactions. 1 Introduction 2 Intramolecular C–N Cross-Dehydrogenative Coupling 2.1 Nitrogen Functionality as Both Coupling Partner and Directing Group 2.2 Chelating-Group-Directed Intramolecular C–N Bond Formation 3 Intermolecular C–N Cross-Dehydrogenative Coupling 3.1 ortho -C–N Bond Formation 3.1.1 Copper-Catalyzed Reactions 3.1.2 Other Transition-Metal-Catalyzed Reactions 3.2 meta - and para -C–N Bond Formation 4 C–N Cross-Dehydrogenative Coupling of Acidic C–H Bonds 5 Conclusions