Photocatalytic Synthesis of Pentafluorosulfanyl Ketones, Acetals, and BCP Motifs Utilizing SF₆

Sulfur hexafluoride (SF₆), a chemically inert and stable gas essential to the electric power industry, poses severe environmental risks due to its persistence and high global warming potential. While traditional degradation methods are inefficient, photocatalytic single electron reduction (SER) enables SF₆ activation into SF₅ radicals, creating opportunities for both degradation and reutilization. The SF₅ group, renowned for its strong electron-withdrawing, lipophilic, and bioisosteric features, has great potential in drug discovery, while efficient methods for synthesizing alkyl- or BCP-SF₅ motifs remain scarce. As a safe, inexpensive, and atom-economical alternative to conventional SF₅ reagents, SF₆ serves as an ideal yet underexplored SF₅ source. Herein, we present a photocatalytic strategy for the direct synthesis of diverse SF₅-containing scaffolds, including ketones, acetals, and bicyclo[1.1.1]pentane derivatives. Derivatization studies demonstrate its synthetic versatility, particularly in accessing α-SF₅-substituted acetaldehydes. Mechanistic and density functional theory (DFT) studies confirm the single electron reduction of SF₆, highlighting a mild, efficient, and broadly applicable route for constructing SF₅-functionalized architectures in fluorinated drug development.