Design plan and reaction development. Amines are a widely abundant functional group in feedstock chemicals and many pharmaceutically relevant molecules. On this basis, we sought to design a technology that builds on previous work by the group that employs Nsulfinyl imine radical acceptors to construct UAAs. We envisioned to develop an approach that allows the exploitation of amines as radical fragments through α-amino C-H bond activation. Here, functionalization is achieved through the creation of C-centered α-amino radicals, which can be generated in three potential pathways depending on the reaction conditions. Firstly, the oxidation-deprotonation pathway involves the photocatalyst oxidizing the nitrogen atom through a single-electron transfer (SET) process, resulting in a nitrogen-centered radical cation. This leads to the significant acidification of the α-amino C-H bond. Subsequently, a base (external or another equivalent of the nonoxidized amine) can deprotonate the α-amino position, resulting in the formation of the desired C-centered α-amino radical. An alternative approach utilizes a direct hydrogen atom transfer (d-HAT) pathway in which the excited state photocatalyst initiates the abstraction of a hydrogen atom from an amine to the excited state photocatalyst. Finally, an indirect hydrogen atom transfer (i-HAT) pathway, which involves an intermediary radical HAT agent, which abstracts a hydrogen atom from the substrate to afford the desired radical fragment. These nucleophilic α-amino radicals are intercepted by an electrophilic radical acceptor, allowing for its efficient coupling with a chiral glyoxylate-derived N-sulfinyl imine. Therefore, we aimed to create α-amino radicals that would react with the chiral N-sulfinyl imine 2 to produce UAAs with high control of the stereoselectivity determining step.