Unlocking Sulfurdiimide Reagents as Radical Traps in the Decarboxylative Synthesis of Sulfinamidines

Aza-sulfur(IV) and (VI) compounds are emerging motifs in medicinal and crop protection chemistry, creating a demand for new methodologies for their challenging synthesis. Sulfurdiimides, the diaza analogues of sulfur dioxide, remain underexplored in their potential to access aza-sulfur compounds, in particular their use as radical traps has not been reported. Here, we describe the synthesis of a new series of stable unsymmetrical sulfurdiimide reagents, which through choice of N-substituent, can be electronically tuned to unlock radical trapping reactivity. Taking advantage of the wide abundance of commercially available carboxylic acids, we have developed an acridine/copper cocatalyzed decarboxylative addition into sulfurdiimide reagents, to deliver a diverse range of sulfinamidine products. The method is scalable, and exhibits good functional group tolerance, and provides an efficient platform to access complex aza-sulfur(VI) functional groups.