Copper‐Enabled Photo‐Sulfonylation of Aryl Halides Using Alkylsulfinates

Abstract A photochemical synthetic method to access sulfones from aryl halides and sodium alkylsulfinates in the presence of CuCl is reported. Regio‐ and chemoselectivity for the sulfonylation is observed for polyhalogenated arenes. Mechanistic studies indicate that a copper sulfinate reagent is formed in situ from CuCl and sodium sulfinate based on NMR experiments. Potential reaction intermediates, including excited state aryl halides are studied using density functional theory calculations and reveal energetically accessible non‐planar triplet geometries.