As morpholine and piperidines are important substructures of many biologically active molecules, our first exploration of simple substrates also included derivatives of these heterocycles. Both N-ethyl morpholine (5) and Nethyl piperidine (6) afforded high yields (98% combined and 99% combined, respectively) of regioisomeric mixtures with a close to statistical preference for ring cyanation to ethyl cyanation (~2:1 ring/ethyl ratio). Furthermore, a common benzylic test substrate in previous publications, tribenzylamine (7) also reacts readily to afford product 7a in 78% assay yield (70% isolated). Overall, these excellent yields are in a similar range as observed in previous publications, suggesting that the new protocol shows reactivity for the synthesis of relatively simple building blocks that is on par with previous reports. Next, we turned our attention to aniline-type substrates (Scheme 3), which we considered to be good model substrates to gain further insights into electronic and steric effects. All aniline substrates employed were reactive under the optimized conditions, with yields ranging between 52% and 84% (Scheme 3). The protocol allows the functionalization of all employed aniline substrates, regardless of the substitution pattern on the arene (MeO vs. p/m-Me vs. p/m-Br vs. NO2) or the aliphatic amine substituents (N-Me vs N-Et vs. N-Pr vs. pyrrolidine).