The intramolecular Fe-catalyzed amination of C–H bonds using azides as nitrene precursors represents an elegant approach toward N-heterocycles. This review summarizes the most recent achievements while focussing on fundamental mechanistic aspects.
An in‐depth study of carbene transfer reactions into polar X−H‐bonds catalyzed by the nucleophilic Fe‐complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) is presented. Whereas alcohols are unreactive, thiols and secondary amines are reactive, silanes showed modest activities. Hammett correlations indicate the presence of an X−H‐acidity dependent mechanistic dichotomy.
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