Neutral Chalcogen Bonding Enabled Photoinduced Cross‐Electrophile C—S/Se Coupling of Aryl Iodides via <scp>S<sub>RN</sub>1</scp> Process
Yongliang Tu, Xiang Li, Bei‐Bei Zhang, Gregory C. Fu, Ling Zhou, Wei Gong, Xiangyu Chen
Abstract
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.