Nitrene transfer catalysts for enantioselective C-N bond formation.

Transition-metal-catalysed, non-enzymatic transformations of C-H and C=C bonds to C-N bonds through nitrene transfer (NT) are powerful synthetic tools to prepare valuable amine building blocks. Although the first examples of racemic NT were reported more than 50 years ago, catalysts that mediate enantioselective NT with a broad substrate scope have been slow to emerge. However, the past ten years have seen the discovery of several first-row, second-row and third-row transition metal catalysts for asymmetric NT. This Review covers recent developments in asymmetric aziridination and C-H bond amination reactions. We describe catalyst design principles, re-evaluate traditional catalyst architectures, show how the scope of nitrene precursors has expanded and present new mechanistic insights. Following this, we highlight remaining opportunities and challenges to developing more practical and general synthetic methodologies. Realizing chemoselective, site-selective and enantioselective intermolecular NT will streamline amine synthesis and allow us to explore new chemical space.