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

The first thiocarboxylation of styrenes and acrylates with CO₂ 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.