Visible-Light-Driven Anti-Markovnikov Hydrocarboxylation of Acrylates and Styrenes with CO_(2)

Light-driven carbon dioxide(CO_(2))capture and utilization is one of the most fundamental reactions in Nature.Herein,we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO_(2).Diverse acrylates and styrenes,including challenging tri-and tetrasubstituted ones,undergo anti-Markovnikov hydrocarboxylation with high selectivities to generate valuable succinic acid derivatives and 3-arylpropionic acids.In addition to the use of stoichiometric aryl thiols,the thiol catalysis is also developed,representing the first visible-lightdriven organocatalytic hydrocarboxylation of alkenes with CO_(2).The UV-vis measurements,NMR analyses,and computational investigations support the formation of a novel charge-transfer complex(CTC)between thiolate and acrylate/styrene.Further mechanistic studies and density functional theory(DFT)calculations indicate that both alkene and CO_(2)radical anions might be generated,illustrating the unusual selectivities and providing a novel strategy for CO_(2)utilization.