New Sustainable Synthetic Routes to Cyclic Oxyterpenes Using the Ecocatalyst Toolbox

Cyclic oxyterpenes are natural products that are mostly used as fragrances, flavours and drugs by the cosmetic, food and pharmaceutical industries. However, only a few cyclic oxyterpenes are accessible via chemical syntheses, which are far from being ecofriendly. We report here the synthesis of six cyclic oxyterpenes derived from ss-pinene while respecting the principles of green and sustainable chemistry. Only natural or biosourced catalysts were used in mild conditions that were optimised for each synthesis. A new generation of ecocatalysts, derived from Mn-rich water lettuce, was prepared via green processes, characterised by MP-AES, XRPD and TEM analyses, and tested in catalysis. The epoxidation of ss-pinene led to the platform molecule, ss-pinene oxide, with a good yield, illustrating the efficacy of the new generation of ecocatalysts. The opening ss-pinene oxide was investigated in green conditions and led to new and regioselective syntheses of myrtenol, 7-hydroxy-alpha-terpineol and perillyl alcohol. Successive oxidations of perillyl alcohol could be performed using no hazardous oxidant and were controlled using the new generation of ecocatalysts generating perillaldehyde and cuminaldehyde.

Automated summary

This study reported the green synthesis of six cyclic oxyterpenes using natural or biosourced catalysts under mild conditions. By epoxidizing ss-pinene and opening the resulting compound, various cyclic oxyterpenes were successfully synthesized, showcasing the efficacy of the new ecocatalysts.