Arguably, the most straightforward approach to this scaffold is via reductive amination of a 2-azine-substituted alkyl ketone. However, due to poor reaction kinetics in the condensation step and/or competitive enamine tautomerization, this method can be capricious for many coupling combinations. Moreover, 2-azine-substituted ketones are rarely readily available and require their own, often cumbersome, syntheses. Beyond this, most approaches to the synthesis of α-alkyl 2-azinyl amines can be divided into two generic classes of reaction that exploit one or two electron processes: (a) 1,2additions of open-and closed-shell nucleophiles to activated 2-azinyl imines (Fig. [i]), and (b) coupling reactions of α-amino radicals with activated 2-azine derivatives (Fig. [ii-iv]). While the former approach has enabled the synthesis of a range of α-alkyl 2-azinyl amine derivatives, these methods often require activation through the incorporation of a high energy auxiliary on the imine nitrogen atom in order to instil the required reactivity towards the nucleophile. The incorporation and removal of this auxiliary adds two further steps to the route required to make the parent α-alkyl 2-azinyl primary amine by this strategy. Furthermore, these approaches often require preformation and isolation of the 2-azinyl imine species. Despite these limitations, perhaps the best-in-class example of this strategy is the use of Ellman sulfinylimines, the 1,2addition reactions of which displays a broad scope in aldimine and organometallic component and also provides an effective means for the synthesis of enantioenriched α-alkyl 2-azinyl amines. Examples of analogous reactions that do not require the use of activating groups on the imine are scarce and display very specific substrate requirements, which limits scope and utility of such reactions. Notable examples of 1,2-additions of alkyl radicals to non-activated 2-azinyl imines were reported by Bode and co-workers, however these were limited to intramolecular examples for the synthesis of 2-azinyl piperidine or piperazine products. Reisman et al. have reported an efficient Ni-catalyzed reductive alkylation of pre-formed N-alkyl 2-azinyl imines, using secondary alkyl or benzyl halides and mediated by a stoichiometric metal reductant, which provided an effective preparation of a range of α-alkyl 2-azinyl secondary amines (Fig. [i]). A ligand centred radical on a Ni-coordinated imine complex is thought to combine with an alkyl radical, forming the N-alkyl 2-azinyl amine after decomplexation. 2-Azinyl-substituted imines, which typically react as electrophiles, could conceivably be used to access α-amino radical species via single electron reduction processes and coupled with electrophilic partners.