Recent Discovery, Development, and Synthetic Applications of Formic Acid Salts in Photochemistry

Abstract The advancement of sustainable photoredox catalysis in synthetic organic chemistry has evolved immensely because of the development of versatile and cost‐effective reagents. In recent years, a substantial effort has been dedicated to exploring the utility of formic acid salts in various photochemical reactions. In this context, formates have demonstrated diverse capabilities, functioning as reductants, sources of carbonyl groups, and reagents for hydrogen atom transfer. Notably, the CO 2 ⋅ – radical anion derived from formate exhibits strong reductant properties for cleaving both C−X and C−O bonds. Moreover, these salts play a pivotal role in carboxylation reactions, further highlighting their significance in a variety of photochemical transformations. The ability of formates to serve as reductants, carbonyl sources, and hydrogen atom transfer reagents reveal exciting possibilities in synthetic organic chemistry. This minireview highlights an array of captivating discoveries, underscoring the crucial role of formates in diverse and distinctive photochemical methods, enabling access to a wide range of value‐added compounds.