Advancing Propylene Epoxidation: the Role of Ethyl Acetate Autoxidation via Cobalt‐Nickel Catalyzed C(acyl)─O Bond Scission

Abstract The selective autoxidation for the synthesis of valuable oxygenates has provoked keen interest from both academic and industrial sectors. Although the generation of reactive oxygen species via oxygen attack on C─H bonds near ester linkages is well‐established, research into aliphatic ester oxidation has primarily focused on combustion, neglecting their potential utility in oxidation processes. Herein, a protocol for producing propylene oxide through the autoxidation of ethyl acetate in tandem with propylene epoxidation is demonstrated. The ethoxy radical, generated by ester C(acyl)─O bond cleavage in situ, subsequently underwent proton‐coupled electron transfer with the Co(OAc)( μ ‐H 2 O) 2 Ni, followed by the formation of the peracetic acid optimally suited for the epoxidation reaction. The research not only eliminates the need for co‐substrates in the epoxidation process but also fills the application gap in bulk‐ester autoxidation, offering insights into the effective utilization of oxy‐intermediates in autoxidation reactions.