Visible‐Light‐Driven Iron‐Promoted Thiocarboxylation of Styrenes and Acrylates with CO2

Abstract The first thiocarboxylation of styrenes and acrylates with CO 2 was realized by using visible light as a driving force and catalytic iron salts as promoters. A variety of important β‐thioacids were obtained in high yields. This multicomponent reaction proceeds in an atom‐ and redox‐economical manner with broad substrate scope under mild reaction conditions. Notably, high regio‐, chemo‐, and diasteroselectivity are observed. Mechanistic studies indicate that a radical pathway can account for the unusual regioselectivity.