Green and Efficient Protocols for the Synthesis of Sulfonyl Fluorides Using Potassium Fluoride as the Sole Fluorine Source

Sulfonyl fluorides are highly versatile organic compounds with diverse applications in click chemistry, biochemistry, and materials science. However, traditional synthetic approaches such as halogen exchange of sulfonyl chlorides using potassium bifluoride (KHF2) face challenges for large-scale production due to KHF2's corrosiveness and reactivity with glassware. Moreover, the instability and limited availability of sulfonyl chlorides as substrates further complicate their synthesis. In this study, we introduce two efficient and environmentally friendly protocols for sulfonyl fluoride synthesis: a stepwise method and a one-pot process. These protocols use stable substrates such as disulfides or thiols, with potassium fluoride as the sole fluorine source and NaOCl·5H2O as the green oxidant. A gram-scale synthesis demonstrates the scalability and efficiency of these protocols. Furthermore, we improved the Davies and Dick method to produce sulfonyl fluorides at ambient temperature in a short time frame. Finally, we showcase various derivatives and transformations of sulfonyl fluorides, highlighting their advantageous reactivity and stability.