S-Trideuteromethylation of Sulfenamides: Redox-Neutral Synthesis of Trideuteromethyl Sulfilimines

This study presents an innovative approach to the synthesis of trideuteriosulfilimines, a class of sulfur(IV)-derived compounds with significant potential in organic synthesis and medicinal chemistry. Our research focused on the modification of sulfenamides and the introduction of a deuterated methyl group, employing an electrophilic trideuteromethylating reagent in an anionic reaction. The method demonstrated broad applicability across various sulfenamides derived from different amides, alkyl amides, and aryl amides, as well as thiol-derived sulfenamides. The reactions generally resulted in excellent yields and high deuteration rates. The study also explored the reaction mechanism, confirming that the process does not proceed via a free radical pathway. This research contributes to the development of efficient and reliable methods for the synthesis of sulfilimines, which are valuable building blocks in organic synthesis and medicinal chemistry.