Multidimensional SuFEx Click Chemistry: Sequential Sulfur(VI) Fluoride Exchange Connections of Diverse Modules Launched From An SOF4 Hub

Sulfur(VI) fluoride exchange (SuFEx) is a new family of click chemistry based transformations that enable the synthesis of covalently linked modules via SVI hubs. Here we report thionyl tetrafluoride (SOF4) as the first multidimensional SuFEx connector. SOF4 sits between the commercially mass‐produced gases SF6 and SO2F2, and like them, is readily synthesized on scale. Under SuFEx catalysis conditions, SOF4 reliably seeks out primary amino groups [R‐NH2] and becomes permanently anchored via a tetrahedral iminosulfur(VI) link: R−N=(O=)S(F)2. The pendant, prochiral difluoride groups R−N=(O=)SF2, in turn, offer two further SuFExable handles, which can be sequentially exchanged to create 3‐dimensional covalent departure vectors from the tetrahedral sulfur(VI) hub.