Aryl Silicon Nucleophiles in Bismuth Catalysis

We present a catalytic protocol utilizing bismuth for the synthesis of aromatic fluorinated thiosulfones, showcasing a seminal example of aryl silicon nucleophiles in Bi catalysis. This catalytic process is enabled by a series of Bi‐based organometallic transformations, including an unprecedented transmetalation of aryl silicates to Bi(III) complexes and the formal migratory insertion of sulfur dioxide (SO 2 ) into the Bi‐C bond. The protocol is compatible with a wide range of anionic and neutral Ar‐Si compounds, including heterocycles. Stoichiometric investigations of individual organometallic steps provide strong evidence supporting a Bi‐redox‐neutral catalytic cycle.