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Epoxidation of Cyclooctene Using Water as the Oxygen Atom Source at Manganese Oxide Electrocatalysts

2019; American Chemical Society; Volume: 141; Issue: 15 Linguagem: Inglês

10.1021/jacs.9b02345

1943-2984

Kyoungsuk Jin, Joseph Maalouf, Nikifar Lazouski, Nathan Corbin, Deng‐Tao Yang, Karthish Manthiram,

Organic Chemistry Cycloaddition Reactions

Epoxides are useful intermediates for the manufacture of a diverse set of chemical products. Current routes of olefin epoxidation either involve hazardous reagents or generate stoichiometric side products, leading to challenges in separation and significant waste streams. Here, we demonstrate a sustainable and safe route to epoxidize olefin substrates using water as the oxygen atom source at room temperature and ambient pressure. Manganese oxide nanoparticles (NPs) are shown to catalyze cyclooctene epoxidation with Faradaic efficiencies above 30%. Isotopic studies and detailed product analysis reveal an overall reaction in which water and cyclooctene are converted to cyclooctene oxide and hydrogen. Electrokinetic studies provide insights into the mechanism of olefin epoxidation, including an approximate first-order dependence on the substrate and water and a rate-determining step which involves the first electron transfer. We demonstrate that this new route can also achieve a cyclooctene conversion of ∼50% over 4 h.