Photocatalytic Synthesis of Pentafluorosulfanyl Ketones, Acetals, and BCP Motifs Utilizing SF ₆

ABSTRACT Sulfur hexafluoride (SF ₆ ), 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 SF ₆ activation into SF ₅ radicals, creating opportunities for both degradation and reutilization. The SF ₅ 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‐SF ₅ motifs remain scarce. As a safe, inexpensive, and atom‐economical alternative to conventional SF ₅ reagents, SF ₆ serves as an ideal yet underexplored SF ₅ source. Herein, we present a photocatalytic strategy for the direct synthesis of diverse SF ₅ ‐containing scaffolds, including ketones, acetals, and bicyclo[1.1.1]pentane derivatives. Derivatization studies demonstrate its synthetic versatility, particularly in accessing α‐SF ₅ ‐substituted acetaldehydes. Mechanistic and density functional theory (DFT) studies confirm the single electron reduction of SF ₆ , highlighting a mild, efficient, and broadly applicable route for constructing SF ₅ ‐functionalized architectures in fluorinated drug development.