Recent Advances in Reactions Involving Carbon Dioxide Radical Anion

Practical photocatalytic hydroalkylation of alkenes with chloroacetates mediated by the formate ion

“…As a reducing agent we decided to apply the formate anion since on the one hand it can serve as a source of hydrogen in the presence of a suitable HAT mediator, and on the other hand, it is a source of the radical anion of carbon dioxide, which is a very strong single electron donor. 32 Moreover, formate salts are benign and cheap low molecular weight regents. As a photocatalyst, 0.5 mol% of the cyanoarene system 3DPA2FBN 33 was used, and the reaction was performed under blue light irradiation.…”

Visible-light-driven alkene dicarboxylation with formate and CO2 under mild conditions

“…Over the past decade, great progress has been made in the catalytic utilization of carbon dioxide (CO 2 ) using visible light. 1 However, many of these transformations require the use of stoichiometric reductant. Recently, we developed an arylcarboxylation of alkenes with CO 2 using formate salt as a low-cost terminal reductant and also as part of the CO 2 source.…”

Thermodynamic H-Abstraction Abilities of Nitrogen Centered Radical Cations as Potential Hydrogen Atom Transfer Catalysts in Y–H Bond Functionalization

“…Therefore, as a type of efficient HAT catalyst or H-abstractor, the hydrogen atom affinity (H-affinity) of X •+ is a significant thermodynamic parameter to quantitatively measure the thermodynamic H-abstraction reactivity of an X •+ and provide valuable guidelines for the application of X •+ in Y–H bond functionalization. − It is well-known that nitrogen centered radical cations (X •+ ) are highly active intermediates. Considering the stability, possible side effects, and resulting concentration of X •+ , the H-affinities of X •+ could not be directly measured by isothermal titration calorimetry or other bond energy measurement methods.…”