Taming Nitrene Reactivity with Silver Catalysts

Nitrene transfer (NT) is a convenient strategy to directly transform C-H bonds into more valuable C-N bonds and exciting advances have been made to improve selectivity. Our work in silver-based NT has shown the unique ability of this metal to enable tunable chemo-, site-, and stereoselective reactions using simple N-dentate ligand scaffolds. Manipulation of the coordination environment and noncovalent interactions around the silver center furnish unprecedented catalyst control in selective NT and provide insights for further improvements in the field. 1 Introduction 1.1 Strategies for Nitrene Transfer 1.2 Brief Summary of Chemocatalyzed Nitrene Transfer 1.3 Focus of this Account 2 Challenges in Chemocatalyzed Nitrene Transfer 2.1 Reactivity Challenges 2.2 Selectivity Challenges 2.3 Chemoselective Nitrene Transfer 2.4 Site-Selective Nitrene Transfer 2.5 Enantioselective Nitrene Transfer 3 Summary and Perspective 3.1 Future Opportunities and Challenges 3.2 Conclusion