The outlined design strategy was investigated using 4-(dimethylamino)benzaldehyde (1a) as the model substrate. Two potential mechanistic scenarios were considered: a sequential oxidation-deprotonation pathway or an i-HAT. Initially, we attempted the reaction under reaction conditions described for a related photocatalytic system; 25 however, no product formation was observed. Through exploration of multiple reaction conditions, we ultimately settled on an oxidation-deprotonation system using [Mes-(OMe)4Acr-Ar]BF4 as photocatalyst in trifluorotoluene, which enabled us to achieve an NMR yield exceeding 95% for the desired α-amino acid derivative 3a.