Peroxydisulfate as an Oxidant in the Site‐Selective Functionalization of sp3 C–H Bonds

The development of methodology for the site‐selective functionalization of sp3 C–H bonds has irrevocably altered the state of organic synthesis. These methods often rely on the use of strong oxidants in conjunction with transition‐metal catalysis. Peroxydisulfate (S2O82–) salts are some of the strongest inorganic oxidants known. They are low‐cost crystalline solids that are stable at room temperature. Harmless sulfate salts are produced as a byproduct of their reactions, allowing S2O82– to serve as a ‘green’ alternative to other commonly employed oxidants. Despite these attractive properties, it has only been in the last ten years that the majority of sp3 C–H functionalization reactions utilizing S2O82– for the diversification of complex molecules have been reported. The objective of this review is to provide a useful reference regarding the recent advancement of sp3 C–H functionalization using S2O82– and to inspire the invention of new protocols utilizing this remarkable oxidant. This review article highlights the use of peroxydisulfate salts for the conversion of sp3 C–H into C–O, C–C, C–N, and C–S bonds. Despite being low‐cost, powerful, and ecologically‐friendly, peroxydisulfate salts remain underutilized in sp3 C–H functionalization reactions. This review will provide a useful reference for researchers interested in developing new reactions with these remarkable oxidants.