The CAzA reaction could also accommodate the use of a ketone to deliver a synthesis of α-2-azinyl α-tertiary amines (ATAs). Molecules bearing an ATA motif -a nitrogen with an adjacent fully substituted carbon atom -are prevalent among pharmaceuticals and bioactive molecules but efficient methods for their synthesis have remained elusive. While the addition of organometallic nucleophiles to N-activated ketimine derivatives is well established, reports of the addition of non-activated organometallics to non-activated all-alkyl ketimines are exceptionally rare. Preliminary investigations guided us towards the use of primary amines for this transformation to overcome the challenging condensation between aliphatic ketones and secondary amines that had yielded none of the desired product in our investigations to date. Surprisingly, we found that ketimines derived from primary benzylamines were uniquely reactive in this process and delivered the α-2-azinyl ATA in modest but synthetically useful yield, given the challenging nature of the transformation (Fig. ). We found that increasing the equivalents of the ketone component and the reaction concentration enabled a range of cyclic and linear ketones (Fig. , 5a-e) to be successfully coupled with 4-methoxybenzylamine ( ) and 2-iodopyridine (3a) to give α-2-azinyl α-tertiary amines (ATAs), 6a-6e. The use of the CAzA method to assemble these sterically congested and functionality-dense amines represents a rare example of C(sp 3 )-rich ATA synthesis by addition of an organometallic nucleophile to non-activated ketimines. Removal of the para-methoxybenzyl (PMB) protecting group from amine 6a was achieved by an oxidative reaction using ceric ammonium nitrate (CAN) under acidic conditions, giving 7a, which demonstrated a streamlined approach to the synthesis of 2-azinyl α,α'-dialkyl primary amines.