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

Article abstract of DOI:10.1002/anie.201611048

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 (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.