In summary, we have developed an operationally straightforward protocol for the synthesis of highly functionalized αalkyl 2-azinyl tertiary amines from readily accessible or commercially available feedstock components. This procedure offers practical access to a complex structural unit that is often challenging to assemble in such a modular fashion. The carbonyl azinylative amination protocol is run under mild and operationally straightforward conditions, enabling a broad scope in all three reaction components. A notable feature of this reaction platform is its independence from the need for a transition metal catalyst, which is usually required to generate a reactive aryl species in other related processes. Beyond the reaction with iminium ions, the 2-azinylation of aldehydes and electron-poor ketones was also realized, under modified conditions, delivering a collection of heterobenzylic alcohols. Additionally, the platform can be adapted to the synthesis of tertiary alcohols containing both di-or trifluoromethyl and heteroaryl substituents, which may be of use in the search for biologically active molecules. Our preliminary studies lead is to believe the reaction invokes a 2-azinyl indium species, which undergoes nucleophilic addition to a C=X electrophile. These findings reveal previously unexplored aspects of the reactivity of heteroleptic 2-azinylindium reagents, which may present further applications of interest to synthetic chemists working in academic and industrial settings.