Other heterocycles were smoothly incorporated into the tertiary amine scaffold, including pyrazine (8o), isoquinoline (8p), furopyridine (8q) and pyrrolopyrimidine (8r) rings, all of which have found a broad utility in drug design and synthesis as pharmacophores for molecular recognition. 3-Iodopyridine (3s) could be used to give amine 8s, albeit in a lower yield to its 2-pyridyl counterpart (8a) offering an interesting insight to the nature of activation of differentially substituted iodo azines; azines with an iodide in the 2-position are more reactive that the 3-iodo and 4-iodo congeners. Pentafluoroiodobenzene (3v) was shown to undergo successful coupling with an iminium to give amine 8v with a perfluorophenyl substituent. This suggests that sufficient electron deficiency of the aromatic ring could preclude the requirement for 2-iodo azines, and possibly expand the scope of this transformation. This hypothesis was supported by the unsuccessful coupling of more electron-rich heteroarenes (see Supplementary Information, Section 7.2). It was noted that with most examples, isolated yields were 5-15% lower than assay yields due to mass loss upon silica gel chromatography, which is commonly encountered with alkylamines. A reaction involving the presence of excess deuterium chloride in a stirred mixture of 1-iodoisoquinoline 3p, indium powder and TMSOTf resulted in the complete conversion to 1-deuteroisoquinoline (1-d-18) (Fig. ). It is notable that stirring the reaction at 70 °C for 20 h was required to achieve complete deuteration. Organoindium species are typically characterised by their mild reactivity and kinetic inertness to deprotonative processes; while the CAzA reaction does not proceed effectively in protic solvent (see Supplementary Information, Table ), it appears that the reactive azinyl indium species does share these properties, to an extent. In the presence of classical hydrogen atom transfer reagents, the reaction still produced exclusively the deuterated product over isoquinoline (18). Given the high calculated electron affinity of the 2-pyridinium radical cation (Int. II, Fig. ) [6.59 eV] (calculated at the BLYP/aug-cc-pVDZ//BLYP/cc-pVDZ level of theory), we can reason that following single electron reduction of the corresponding TMS-activated 2-iodo-azinium cation (Int. I), a successive single electron reduction process to generate the organoindium reagent (Int. III) would outcompete undesired HAT to quench the azinium radical cation. Together, these data suggest that the formation of a putative