Stereoselective C  N Bond‐Forming Reactions Through C ( sp 3 ) H Bond Insertion of Metal Nitrenoids

Direct catalytic C(sp3)–H functionalization with metal-nitrenoid species as key intermediates is a straightforward strategy for the formation of C(sp3)N bonds. Over the past decade significant progress has been made in asymmetric nitrene C(sp3)–H insertions. Inter- and intramolecular processes starting either from iminoiodinanes, azides, or N-sulfonyloxycarbamates as nitrene precursors have been reported using mainly chiral rhodium but also ruthenium and manganese catalysts. These asymmetric C–H amination reactions proceed with good to high stereoselectivities, thereby providing access to benzylic and allylic amines as key building blocks for the synthesis of relevant molecules for biological studies.