A tungsten-based polyoxometalate catalyst employing aqueous H2O2 as a benign oxidant has been used for the solvent free catalytic epoxidation of the trisubstituted alkene bonds of a wide range of biorenewable terpene substrates. This epoxidation protocol has been scaled up to produce limonene oxide, 3-carene oxide and α-pinene oxide on a multigram scale, with the catalyst being recycled three times to produce 3-carene oxide. Epoxidation of the less reactive disubstituted alkene bonds of terpene substrates could be achieved by carrying out catalytic epoxidation reactions at 50 °C. Methods have been developed that enable direct epoxidation of untreated crude sulfate turpentine to afford 3-carene oxide, α-pinene oxide and β-pinene oxide. Treatment of crude epoxide products (no work-up) with a heterogeneous acid catalyst (Amberlyst-15) results in clean epoxide hydrolysis to afford their corresponding terpene-anti-diols in good yields.
Bull, S., Cunningham, W., Tibbetts, J., Hutchby, M., Smug, K. A., Davidson, M., Hintermair, U., & Plucinski, P. (2020). Sustainable Catalytic Protocols for the Solvent Free Epoxidation and (anti)-Dihydroxylation of the Alkene Bonds of Biorenewable Terpene Feedstocks Using H2O2 as Oxidant. Green Chemistry, 22(2), 513-524. https://doi.org/10.1039/C9GC03208H