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.

过渡金属催化的非酶促 C-H 和 C=C 键通过氮烯转移 (NT) 转化为 C-N 键是制备有价值的胺结构单元的强大合成工具。尽管 50 多年前就报道了第一个外消旋 NT 的例子，但介导具有广泛底物范围的对映选择性 NT 的催化剂却迟迟没有出现。然而，在过去的十年中，已经发现了几种用于不对称 NT 的第一行、第二行和第三行过渡金属催化剂。本综述涵盖了不对称氮丙啶化反应和 C-H 键胺化反应的最新进展。我们描述了催化剂的设计原则，重新评估了传统的催化剂结构，展示了氮烯前体的范围是如何扩展的，并提出了新的机理见解。按照此，我们强调了开发更实用和通用的合成方法的剩余机遇和挑战。实现化学选择性、位点选择性和对映选择性分子间 NT 将简化胺合成，并使我们能够探索新的化学空间。