The conversion of C‒H bonds to C‒N bonds offers a sustainable and economical strategy for the synthesis of nitrogen-containing compounds. However, challenges regarding the control of regio- and stereoselectivity currently limit the broad applicability of intermolecular C(sp³)‒H amination reactions. We address these restrictions by directed nitrene-mediated C‒H insertion using a metal-coordinating functional group. We report a highly stereocontrolled, iron-catalysed direct α-amination of abundant carboxylic acid feedstock molecules. The method provides in a single step high-value N-Boc-protected α-monosubstituted and α,α-disubstituted α-amino acids, which can then be immediately used for applications including solution- and solid-phase peptide synthesis. This method fulfils important aspects of sustainability by being highly step efficient and utilizing non-toxic, Earth-abundant iron as the catalytic metal.

将 C-H 键转化为 C-N 键为合成含氮化合物提供了一种可持续且经济的策略。然而，目前关于区域选择性和立体选择性控制的挑战限制了分子间 C( sp ³ )-H 胺化反应的广泛适用性。我们通过使用金属配位官能团定向氮烯介导的 C-H 插入来解决这些限制。我们报告了丰富的羧酸原料分子的高度立体控制、铁催化的直接 α-胺化。该方法一步提供高价值N-Boc 保护的 α-单取代和 α,α-二取代 α-氨基酸，然后可立即用于溶液和固相肽合成等应用。这种方法通过高效的步骤和利用无毒的、地球上丰富的铁作为催化金属，实现了可持续性的重要方面。