Photoredox Catalytic Activation of Sulfur Hexafluoride for Pentafluorosulfanylation of α‐Methyl‐ and α‐Phenyl Styrene

Abstract Sulfur hexafluoride is inert, non‐toxic, and cannot simply be applied as pentafluorosulfanylation reagent. We present the first photoredox catalytic way to convert it into pentafluorosulfanylated α‐methyl and α‐phenyl styrenes simply by using light. The work tackles the challenges of precise activation of sulfur hexafluoride by a photoredox catalyst with designed consecutive electron transfer cycles in a fashion that styrenes trap the generated pentafluorosulfanyl radical. The method overcomes the highly problematic access to vinylic and allylic pentafluorosulfanyl styrenes and combines it with the disposal of the most potent greenhouse gas. Together with the use of light as energy source, an exceptionally high level of sustainability is gained.