In 2020, our group disclosed carbonyl alkylative amination (CAA) method for tertiary alkylamine synthesis (Fig. ). Through this visible light-mediated process, a range of alkyl radicals add to in situ generated all-alkyl-iminium ions and the resulting aminium radical cation undergoes rapid hydrogen atom transfer (HAT) with a silane to form the tertiary alkylamine product, released after workup. This transformation allows for remarkably facile access to an array of complex amines from abundant and diverse building blocks and can be extended to the synthesis of α-tertiary amino acid derivatives and α-fluoromethyl tertiary amines. Continuing the evolution of the generic CAA strategy, we speculated that leveraging 2-iodo azines, as precursors to heteroarene radical coupling partners, may be amenable to this photochemical protocol and provide a convenient means to generate α-alkyl 2-azinyl amines. We recognized that the generation of a 2-azinyl radical under the mild reaction conditions used for the alkyl radicals would be substantially more challenging due to the higher energy nature of the heteroaryl radical species. Indeed, our extensive preliminary studies were largely unsuccessful, with only a modest yield of the desired α-alkyl 2-azinyl amine 4a obtained (Fig. ). In the proposed mechanism for the visible light-mediated CAA reaction tris(trimethylsilyl)silane [(Me3Si)3Si-H] fulfils a multifaceted role: it is integral to radical initiation, quenches the aminium radical cation on the amine nitrogen atom after radical addition to the iminium ion and carries the radical chain through halogen atom transfer (XAT) with the alkyl iodide. We speculated that the poor outcome of the CAzA reaction under these conditions was due to rapid, competitive hydrogen atom transfer (HAT) of the 2-pyridyl radical (BDE of pyridine ~ 100 kcal mol -1 ) with (Me3Si)3Si-H (BDE = 84 kcal mol -1 ). To avoid the use of (Me3Si)3Si-H, and guided by the pioneering studies of Rieke on the formation of heteroleptic alkylzinc reagents, we initially considered that a stronger single electron reducing agent might facilitate the formation of the desired 2-pyridyl radical from the parent 2-iodo pyridine. However, in line with the observations of Rieke, then subsequent reduction of the incipient heteroaryl radical with a second equivalent of a metal may lead to the corresponding 2-pyridyl organometallic species, which has not previously been explored in terms of its reactivity towards electrophilic all-alkyl iminium species, to the best of our knowledge.