Dehydrogenative Imination of Low-Valent Sulfur Compounds—Fast and Scalable Synthesis of Sulfilimines, Sulfinamidines, and Sulfinimidate Esters

[Image: see text] Herein, we describe an electrochemical pathway for the synthesis of sulfilimines, sulfoximines, sulfinamidines, and sulfinimidate esters from readily available low-valent sulfur compounds and primary amides or their analogues. The combination of solvents and supporting electrolytes together act both as an electrolyte as well as a mediator, leading to efficient use of reactants. Both can be easily recovered, enabling an atom-efficient and sustainable process. A broad scope of sulfilimines, sulfinamidines, and sulfinimidate esters with N-EWGs is accessed in up to excellent yields with broad functional group tolerance. This fast synthesis can be easily scaled up to multigram quantities with high robustness for fluctuation of current densities of up to 3 orders of magnitude. The sulfilimines are converted into the corresponding sulfoximines in an ex-cell process in high to excellent yields using electro-generated peroxodicarbonate as a green oxidizer. Thereby, preparatively valuable NH sulfoximines are accessible.