Direct Electrocatalytic O-O Coupling for Modular Synthesis of Aza-cyclic Peroxides from Paired Oxygen Donors

Abstract

Organic peroxidic bonds represent privileged scaffolds in both organic and medicinal chemistry. However, direct construction of peroxidic bonds (O-O) remains unreported in synthetic methodology, as conventional strategies rely on preactivated inorganic peroxo units derived from exogenous oxidants and oxygen sources, followed by their assembly onto organic molecules—approaches exhibiting inherent limitations in compatibility and safety. Herein, we present the utilization of low-cost and easily accessible oximes and enamides as paired oxygen donors. Under electrochemical oxidation, these substances directly generate oxygen species that are amenable to coupling, thereby enabling the formation of novel endoperoxides, specifically five-membered aza-peroxide rings, under mild and environmentally friendly catalytic conditions.