Search for: All records

Abstract Transition metal‐catalyzed, non‐enzymatic nitrene transfer (NT) reactions to selectively transform C−H and C=C bonds to new C−N bonds are a powerful strategy to streamline the preparation of valuable amine building blocks. However, many catalysts for these reactions use environmentally unfriendly solvents that include dichloromethane, chloroform, 1,2‐dichloroethane and benzene. We developed a high‐throughput experimentation (HTE) protocol for heterogeneous NT reaction mixtures to enable rapid screening of a broad range of solvents for this chemistry. Coupled with the American Chemical Society Pharmaceutical Roundtable (ACSPR) solvent tool, we identified several attractive replacements for chlorinated solvents. Selected catalysts for NT were compared and contrasted using our HTE protocol, including silver supported byN‐dentate ligands, dinuclear Rh complexes and Fe/Mn phthalocyanine catalysts. 

Transition metal-catalyzed asymmetric nitrene transfer is a powerful method to generate enantioenriched amines found in natural products and bioactive molecules. 

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