Electrocatalytic Synthesis of Dithiosulfonates From Tetrasulfides and Sodium Arylsulfinates

ABSTRACT

Sustainable unsymmetrical disulfide synthesis is of significant interest due to the crucial role of disulfide bonds in protein stabilization, peptide drug design, and medicinal chemistry, as exemplified by Disulfiram and ADT‐OH. Additionally, sulfone‐containing compounds such as Eletriptan and Dapsone exhibit important pharmaceutical activities. Combining these two motifs, dithiosulfonates (compounds containing a S–S–S(O) ₂ linkage) represent a class of compounds with high research potential. Traditional methods for unsymmetrical disulfide synthesis suffer from malodorous thiols, overoxidation, toxicity, and reliance on precious metals. Although pre‐activation strategies using RSSTs reagents have enabled efficient cross‐coupling, the preparation of RSSTs themselves remains challenging, with conventional routes suffering from low atom economy and toxicity, while photocatalytic approaches require expensive iridium catalysts. Herein, we report a mild, transition‐metal‐free electrochemical approach for the synthesis of dithiosulfonates from tetrasulfides and sodium arylsulfinates. This method avoids malodorous thiols, toxic reagents, and precious metal catalysts, providing a greener and more sustainable route to structurally diverse dithiosulfonates.