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DFT calculations and kinetic analysis have been employed to comprehensively explore the possibility to prepare epoxides by one‐step method using the in‐situ generated peroxy radicals or hydroperoxides as epoxidizing agents. Computational studies demonstrated that the selectivities for the reaction systems of O2/R2/R1, O2/CuH/R1, O2/CuH/styrene, O2/AcH/R1 were 68.2%, 69.6%, 100% and 93.3%, respectively...
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