Herein, we report the development of an operationally straightforward and general multicomponent method that addresses some of the key strategic gaps in the synthesis of α-alkyl 2-azinyl amines (Fig. ). In this modular reaction, an iminium ion, which is generated in situ from an aldehyde and a secondary amine, is coupled with a 2-iodo azine via the intermediacy of a putative 2-azinyl indium nucleophile (also generated in situ). A broad range of tertiary amine products containing many pharmaceutically-relevant structural and functional features can be formed via these tandem C-N and C-C bond forming steps from abundant amine and carbonyl feedstocks and readily available 2-iodo azines. This work also reveals the underexplored utility of a 2-azinyl-anion equivalent that we believe manifests in the form of the organoindium species, and which is demonstrated through its reactions with other common synthetically versatile functionalities. Considering the demonstrated importance and interest in nitrogen-rich scaffolds, we believe these methods will be of substantial interest to the synthetic community in both industrial and academic settings.