Direct and mild C-H functionalizations of complex substrates with control of site selectivity is one of the key goals for catalyst development in the field. Methods that introduce new C-C bonds in molecules exhibiting basic amine functionalities are particularly rare and frequently not general enough for late stage functionalization of complex substrates. Among the existing methods for C-H functionalization, the α-C-H cyanation of basic amines is particularly valuable, as the introduced cyanide group can subsequently be converted into various different functionalities. Therefore, α-C-H cyanated amines are valuable synthetic intermediates, for example for the synthesis of α-amino acids. One general trend in the α-C-H cyanation of amines is that aniline-type structures appear to be more reactive, possibly due to the lower bond dissociation energy of the functionalized α-C-H bond. In comparison, α-C-H cyanations of tertiary amines with unactivated (not benzylic or aniline-type) α-C-H bonds are not as well established. Diverse reactivity platforms have been reported to achieve this overall transformation. The existing protocols can be electrochemically driven, photoredox-catalyzed, Mn and Fe catalyzed, ClO 2 driven, or photochemical ; they also include a non-metal mediated process employing KSCN as cyanation reagent . One common thread in all these methods is that they rely on free radical intermediates (Scheme 1A/B), which inherently limits their functional group tolerance. In an interesting extension of this principle, allyl amines can undergo α-C-H cyanation in the presence of t BuOOH/FeCl 2 (typical conditions that allow α-C-H cyanation), but then subsequently undergo functionalization at the olefin.