A method for electrophilic (fluoroalkyl)­sulfenylation of nucleophiles by collaborative CTAB- and squaric acid-promoted deoxygenation of sulfonyl derivatives is reported. Mechanistic studies indicate that squaric acid dramatically decreased the energy barrier in the first step of deoxygenation. The mild deoxygenation process enables the reduction of a wide range of functionalized sulfonyl chlorides as well as sulfonic anhydrides. The novel method represents an operationally simple protocol using readily available reagents and exhibits broad functional group tolerance.

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Polythioamide is a unique type of sulfur-containing polymers with advanced functionalities. However, current synthetic approaches based on elemental sulfur, which could easily react with unsaturated functional groups, restrict the choice of substrates. Inspired by the highly efficient sulfur-fluoride exchange(SuFEx) polymerization through discrete hubs, we here report a novel and general method for the synthesis of polythioamides from diboronic acids, secondary diamines, and thiocarbonyl fluoride as the connective hub. Well-defined structures, including previously inaccessible unsaturated substrates, were realized with a narrow polydispersity. The polythioamides can efficiently and selectively bind to metal ions and were applied in precious metal recovery. Further development results in PdII-crosslinked single-chain nanoparticles acting as a recyclable homogeneous catalyst, demonstrating promising applications of these unprecedented polythioamides. We anticipate that thiocarbonyl fluoride could be a powerful hub for the challenging synthesis of sulfur-containing polymers.