Enantioselective synthesis of sulfondiimidoyl fluorides via pyridine-N-oxide-catalyzed sulfondiimidoyl transfer.

Sulfondiimidoyl fluorides are valuable chiral SuFEx connectors, yet their catalytic asymmetric synthesis is challenging due to poor discrimination between two similar sulfilimino groups. Herein, we disclose a highly efficient catalytic asymmetric synthesis via pyridine-N-oxide-catalyzed sulfondiimidoyl transfer. From racemic sulfinamidines, in situ chlorination affords the sulfondiimidoyl chlorides, which undergo asymmetric Cl-F exchange promoted by chiral ArPNO C4 using TMAF as the fluoride source, delivering products in up to 90% yield and 92% ee. Mechanistic studies support a covalent activation pathway with a dynamic kinetic asymmetric transformation, and utility is demonstrated by SuFEx reactions with C/O/N nucleophiles. This work provides a practical route to chiral sulfondiimidoyl fluorides and opportunities for advancing asymmetric sulfondiimidoyl transfer catalysis.