Neutral Chalcogen Bonding Enabled Photoinduced Cross‐Electrophile C—S/Se Coupling of Aryl Iodides via <scp>S_RN1</scp> Process

Comprehensive Summary Cross‐coupling reactions between aryl halides and thiolates or selenolates typically require transition metals, photocatalysts, strong bases, or/and malodorous thiols/selenols, with various mechanisms proposed. This study aims to leverage a new application of neutral ChB to address these challenges and enable a very simple photoinduced cross‐electrophile C—S/Se coupling using readily available chalcogen electrophiles. Mechanistic investigations have revealed the important role of neutral ChB in facilitating single electron transfer processes, thereby enabling the generation of thiolates/selenolates from stable chalcogen electrophiles and α ‐aminoalkyl radicals, which possess the capability to abstract halogen atoms from aryl iodides. Moreover, the study provided support for the radical nucleophilic substitution mechanism.