Radiation-induced aerobic oxidation via solvent-derived peroxyl radicals

Abstract

Oxidation is a fundamental transformation in synthesis. Developing facile and effective aerobic oxidation processes under ambient conditions is always in high demand. Benefiting from its high energy and good penetrability, ionizing radiation can readily produce various reactive species to trigger chemical reactions, offering another option for synthesis. Here, we report an ionizing radiation-induced aerobic oxidation strategy to synthesize oxygen-containing compounds. We discovered that molecular oxygen (O₂) could be activated by reactive particles generated from solvent radiolysis to produce solvent-derived peroxyl radicals (R_solOO·), which facilitated the selective oxidation of sulfides and phosphorus(III) compounds at room temperature without catalysts. Density functional theory (DFT) calculations further revealed that multiple R_solOO· enable the oxidation reaction through an oxygen atom transfer process. This aerobic oxidation strategy broadens the research scope of radiation-induced chemical transformations while offering an opportunity to convert nuclear energy into chemical energy.