Late‐Stage Heteroarylation of Hetero(aryl)sulfonium Salts Activated by α‐Amino Alkyl Radicals

Abstract We report a late‐stage heteroarylation of aryl sulfonium salts through activation with α‐amino alkyl radicals in a mechanistically distinct approach from previously reported halogen‐atom transfer (XAT). The new mode of activation of aryl sulfonium salts proceeds in the absence of light and photoredox catalysts, engaging a wide range of hetarenes. Furthermore, we demonstrate the applicability of this methodology in synthetically useful cross‐coupling transformations.