Multidimensional SuFEx Click Chemistry: Sequential Sulfur(VI) Fluoride Exchange Connections of Diverse Modules Launched From An SOF 4 Hub

Sulfur(VI) fluoride exchange (SuFEx) is a new family of click chemistry based transformations that enable the synthesis of covalently linked modules via S VI hubs. Here we report thionyl tetrafluoride (SOF 4 ) as the first multidimensional SuFEx connector. SOF 4 sits between the commercially mass‐produced gases SF 6 and SO 2 F 2 , and like them, is readily synthesized on scale. Under SuFEx catalysis conditions, SOF 4 reliably seeks out primary amino groups [R‐ NH 2 ] and becomes permanently anchored via a tetrahedral iminosulfur(VI) link: R−N=(O=)S(F) 2 . The pendant, prochiral difluoride groups R−N=(O=) SF 2 , 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.