Synthesis of Aza‐S(VI) Fluorides and Primary Sulfonimidamides from Sulfinylamines

Abstract Aza‐S(VI) fluorides are crucial compounds in the synthesis of various S(VI) derivatives, which find broad applications in drug discovery. However, the synthesis of sulfonimidoyl and sulfondiimidoyl fluorides have been relatively underexplored, often requiring lengthy reaction sequences and/or the use of hazardous gaseous reagents. In this study, we present a rapid one‐pot method for producing sulfonimidoyl fluorides from sulfinylamines via a nucleophilic addition/electrophilic fluorination sequence. Similarly, sulfondiimidoyl fluorides can be synthesized using the same sequence, preceded by the formation of unsymmetrical sulfurdiimides readily generated in situ from sulfinylamines. Whereas isolation of sulfondiimidoyl fluorides was not feasible, they could be efficiently converted into primary sulfonimidamides by base hydrolysis in a one‐pot process. Furthermore, we explored the reactivity of aza‐S(VI) fluorides with various nucleophiles, demonstrating a versatile synthetic platform for the synthesis of aza‐S(VI) compounds.