Recent mechanistic work in the Fe catalyzed α-C-H oxidation of tertiary amines has uncovered a radical rebound (instead of a free radical) mechanism by which tertiary aliphatic amines can undergo α-C-H functionalization. We speculated that this reaction manifold could enable α-C-H cyanations with greater functional group tolerance than methods mediated by free radicals and thus be valuable for late-stage functionalization approaches in complex molecular settings (Scheme 1C). This manuscript details reaction optimizations and substrate scope studies employing this approach to establish a general catalyst system for the late-stage functionalization of tertiary amine substrates. The protocol tolerates the presence of double bonds, triple bonds, unprotected alcohols and ketones, five-and six-membered heterocycles, and various other functional groups. To the best of our knowledge, the reported protocol is the most general approach to the α-C-H cyanation of tertiary amines reported to date.