Visible Light/Copper Catalysis-Enabled Arylation and Alkenylation of Phosphorothioates via Site-Selective C-H Thianthrenation.

An efficient visible light/copper-enabled arylation and alkenylation of phosphorothioates with thianthrenium salts via a C(sp)-S cross-coupling reaction have been demonstrated. This strategy uses aryl/alkenyl thianthrenium salts as new electrophilic reagents, which can be easily prepared by the site-selective C-H thianthrenation of arenes/alkenes with high regioselectivity. Mechanistic studies revealed a crucial role of the in situ formed copper-sulfur complex, which undergoes a facile SET process with the thianthrenium salts under visible light conditions, thereby successfully achieving the desired cross-coupling reactivity.