CH Functionalization via Asymmetric Nitrene Transfer

Abstract The prevalence of amines in natural products and pharmaceuticals has stimulated interest in efficient, asymmetric methods to transform CH to CN bonds. Transition metal‐supported nitrene intermediates can undergo ready insertion into a variety of CH bonds via nitrene transfer (NT), provided the chemo‐, site‐, and enantioselectivity can be controlled in a predictive manner. In recent years, the field of transition metal‐catalyzed asymmetric nitrene transfer has grown rapidly with the design of new ligand scaffolds and the addition of a host of biocatalysts to the catalog of catalysts able to furnish diverse enantioenriched amine products. This article focuses on the recent advances in the arena of both intra‐ and intermolecular asymmetric CH aminations. The key differences between the types of catalysts utilized in asymmetric CH functionalization via NT will be highlighted, both in terms of the metal identity and ligand design. The article is organized by metal identity and concludes with a discussion of areas where opportunities and challenges still remain in the field.