Sulfoximines are promising compounds in both organic synthesis and drug development. An area of interest in sulfoximine chemistry is the formation of N-arylated sulfoximines. Previous approaches either require strong oxidizing agents to oxidize species such as sulfilimines or had limited scope for direct N-H arylation. A photoredox dehydrogenative Chan-Lam coupling of free diaryl sulfoximines and arylboronic acids has been shown to have a good diversity of functional groups on both the sulfoximines and arylboronic acid as well as to not require an external oxidant. Mechanistic investigations and DFT calculations give insight into this coupling. Initially, a stoichiometric phase occurs converting the copper(II) to copper(I). The N-arylated sulfoximine product and the NH-sulfoximine substrate are able to serve as ligands for the produced copper(I). The ligated copper complex is a photocatalyst, which is able to reduce NH-sulfoximine by a single electron transfer, circumventing the need for an oxidant. The thermodynamic cycle between possible photocatalysts was explored. Following the oxidation of the copper, the NH-sulfoximine is deprotonated forming hydrogen gas in the process. Possible pathways were probed for the formation of the H<sub>2 </sub>gas. These mechanistic insights provide a basis for future designs of systems for the formation of C-N bonds.

Photoredox autocatalytic Chan Lam coupling of free diaryl sulfoximines

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