Photoiodocarboxylation of Activated CC Double Bonds with CO₂ and Lithium Iodide

The photolysis at 254 nm of lithium iodide and olefins 1 carrying an electron-withdrawing Z-substituent in CO₂-saturated (1 bar) anhydrous acetonitrile at room temperature produces the atom efficient and transition metal-free photoiodocarboxylation of the CC double bond. The reaction proceeds well for terminal olefins 1 to form the new C–I and C–C σ-bonds at the α and β-positions of the Z-substituent, respectively, and is strongly inhibited by polar protic solvents or additives. The experimental results suggest that the reaction channels through the radical anion [CO₂^•–] in acetonitrile, yet involves different intermediates in aqueous medium. The stabilizing ion-quadrupole and electron donor–acceptor interactions of CO₂ with the iodide anion play a crucial role in the reaction course as they allow CO₂ to penetrate the solvation shell of the anion in acetonitrile, but not in water. The reaction paths and the reactive intermediates involved under different conditions are discussed.