Finally, we also explored if secondary amines Et 2 NH 28 and i Pr 2 NH 31 can undergo analogous α-C-H cyanation under the optimized conditions (Scheme 5). In contrast to a previously reported reaction protocol demonstrating clean α-C-H cyanation of secondary amines via a photoredox-catalysis, the herein described Fe catalyzed protocol is not successful in promoting this transformation. Instead, benzamide 30 is obtained in 86% yield when Et 2 NH 28 is employed as substrate. 30 is likely formed by amidation of the peroxyester oxidant. As established in the substrate scope using complex amines substrates (Scheme 4), amides do not undergo further α-C-H cyanation. Scheme 4. Substrate Scope of Complex Amines and Drug Substrates. Assay yields are provided together with isolated yield in brackets.