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

Abstract

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

Key words

amination - amines - amides - cross-coupling - dehydrogenation - transition metals

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