General Photo-Driven Chemoselective and Rapid Hydropentafluorosulfanylation of Alkenes via an Orchestrated Radical...

Although chain propagation strategies could accelerate molecular synthesis (e.g., Kharasch-type additions of fluorinated haloalkanes), controllable radical processes remain challenging. Herein, we develop a novel metal-free radical chain transformation that integrates radical addition, hydrogen atom transfer, and halogen atom transfer to enable hydropentafluorosulfanylation of alkenes. Our method exhibits a broad substrate scope across 73 substrates, including both activated and nonactivated alkenes, alkenes derived from natural products, and pharmaceutically relevant alkenes. This versatility enables the rapid synthesis of structurally diverse SF₅-functionalized molecules. The biological and pharmaceutical applications are highlighted and demonstrated through cellular and in vivo experiments, thereby showcasing the synthetic utility of the developed methodology.