Iron‐catalyzed C−H amination is emerging as an attractive and sustainable method to install amine functionalities into organic compounds. Amination of C(sp3)−H bonds is usually mediated by an iron‐nitrene intermediate via a Hydrogen Atom Abstraction/Radical Recombination mechanism reminiscent of biomimetic C−H oxidation. Accordingly, this transformation can be catalyzed by engineered iron enzymes, heme and nonheme iron complexes as well as iron salts, although it is often limited to intramolecular reactions and/or activated positions. Aromatic C(sp2)−H amination is mediated by addition of electrophilic iron nitrenes or protonated N‐radical intermediates (produced with Fe catalysts) to aromatic systems. Again, high selectivity is obtained via (pseudo) intramolecular reactions. From a mechanistic perspective, several iron nitrene intermediates have been isolated and characterized over the years in different ligand scaffolds and iron oxidation states. Structure‐activity correlations have been drawn only in few cases and point to a key role of the spin density on the nitrene ligand and of the iron oxidation state. This review describes the state of the art for homogeneous iron catalyzed C(sp3)−H and C(sp2)−H amination focusing on the last 5 years (2019–2023) from a mechanism‐driven catalyst design perspective.

Dario Possenti

Giorgio Olivo

ChemCatChem

CHEMCATCHEM 的影响因子为 4.495 (2018)，是催化领域的顶级期刊之一。该杂志提供关于异相、均相以及生物和纳米催化的主要研究论文和重要的辅助信息。该杂志很好地加强了这些社区之间的交叉交流。它的作者和读者来自世界各地的学术界、化学工业和政府实验室。它代表欧洲化学协会出版，该协会由 16 个欧洲化学学会组成，并得到德国催化学会的支持。

ChemCatChem is one of the leading journals in the field of catalysis, with an impact factor of 4.495 (2018). The journal publishes major research papers and important supplementary information on heterogeneous, homogeneous, and biocatalysis as well as nanocatalysis. It effectively enhances cross-communication among these communities, attracting authors and readers from academia, the chemical industry, and government laboratories worldwide. The journal is published by the European Chemical Society, which comprises 16 European chemical societies, and is supported by the German Catalysis Society.

CHEMCATCHEM 是催化领域的顶级期刊之一，影响因子为 4.495（2018 年）。该杂志主要发表关于异相催化、均相催化以及生物和纳米催化的研究论文，并提供重要的辅助信息。它促进了这些领域之间的交叉交流，吸引了来自全球学术界、化学工业和政府实验室的作者和读者。该期刊由欧洲化学协会出版，该协会由 16 个欧洲化学学会组成，并得到德国催化学会的支持。

Category	Quartile
化学	3
化学, 物理化学	3

Homogeneous Iron Catalyzed C−H Amination

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Category	Quartile
CHEMISTRY, PHYSICAL	2