Photo‐/Electrochemically Radical Cation‐/Anion‐Mediated Defluorinative Functionalization of Organofluorides

Radical cation‐ or anion‐based defluorinative functionalization has rapidly emerged as a highly effective method for enhancing molecular complexity, with widespread applications in medicinal chemistry and materials science. Photo‐/electrochemistry, as green and sustainable approaches, enable diverse chemical transformations. Remarkable achievements in photo(electro)chemical defluorinative functionalization of radical cations or anions is reported. The generation of radicals via defluorination of organofluorides occurs through three main mechanistic pathways: single‐electron reduction, spin center shift, and single‐electron oxidation. This review comprehensively summarizes recent advances in reactions involving photochemically, electrochemically, or photoelectrochemically initiated radical cation or anion CF functionalization of organofluorides to forge a CC or CX (X = N, B, O, S, or Se) bond. This review highlights challenges and identifies potential areas for improvement. Additionally, the full spectrum of photocatalysts applied in this strategy, including metal‐based and organic photoredox catalysts, is reviewed in detail.