Discovery of a simple iron catalyst reveals the intimate steps of C–H amination to form C–N bonds

Formation of ubiquitous C-N bonds traditionally uses prefunctionalized carbon precursors. Recently, metal-catalyzed amination of unfunctionalized C-H bonds with azides has become an attractive and atom-economic strategy for C-N bond formation, though all catalysts contain sophisticated ligands. Here, we report Fe(HMDS)2 (HMDS = N(SiMe3)2-) as an easy-to-prepare catalyst for intramolecular C-H amination. The catalyst shows unprecedented turnover frequencies (110 h-1vs. 70 h-1 reported to date) and requires no additives. Amination is successful for benzylic and aliphatic C-H bonds (>80% yield) and occurs even at room temperature. The simplicity of the catalyst enabled for the first time comprehensive mechanistic investigations. Kinetic, stoichiometric, and computational studies unveiled the intimate steps of the C-H amination process, including the resting state of the catalyst and turnover-limiting N2 loss of the coordinated azide. The high reactivity of the iron imido intermediate is rationalized by its complex spin system revealing imidyl and nitrene character.