New Sustainable Synthetic Routes to Cyclic Oxyterpenes Using the Ecocatalyst Toolbox

Abstract

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-α-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.

Mechanochemistry and Eco-Bases for Sustainable Michael Addition Reactions

“…The Grison group has shown that the remediation phytotechnologies, such as phytoextraction [ 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ], rhizofiltration [ 28 , 29 , 30 , 31 ] and biosorption [ 32 , 33 , 34 , 35 , 36 ] generate biomass which can be turned into innovative ecocatalysts. Among the plant species that can be transformed, here, we selected the ones that were the richest in potassium ( Figure 1 ).…”

Green and Effective Preparation of α-Hydroxyphosphonates by Ecocatalysis

“…This innovative methodology is based on the use of biomass derived from metal-hyperaccumulating plants, used in the phytoextraction of metal contaminated sites, for the preparation of polymetallic catalysts suitable for applications in organic synthesis. This concept was successfully applied for important transformations such as the Lewis and/or Brønsted acid-catalyzed reactions (Diels–Alder reaction, Friedel–Crafts reaction, multicomponent reactions, cascade reactions) [ 54 , 55 , 56 , 57 , 58 ]; coupling reactions (Suzuki, Heck, Sonogashira and Ulmann type reactions) [ 59 , 60 , 61 , 62 , 63 , 64 ]; reductions (aminoreduction, selective reduction of αβ-unsaturated carbonyl compounds, nitro- and halogeno arenes) [ 65 , 66 , 67 ]; oxidations (epoxidations, oxidative cleavage, oxidations of alcohols) [ 68 , 69 , 70 ]; and tandem reactions (tandem carbonyl-ene cyclization, synthesis of substituted pyridines and oxidative iodination of ketones) [ 71 , 72 , 73 ]. However, examples on the use of ecocatalysis for C-P bond formation have not been reported.…”

Obtaining cumin (Cuminum Cymminum) essential oils by steam distillation. Part I: investigation of operation parameters on essential oil yield and distribution of oil composition

“…9,[12][13][14][15] Perillyl alcohol can be converted to perillaldehyde and then to cumin aldehyde with the help of ecocatalyst. 16 Steam distillation is typically used to obtain essential oils. Despite being a traditional method, steam distillation has some advantages over other methods.…”

“…Preliminary clinical and clinical studies have demonstrated that perillyl alcohol is successful in fighting even the most aggressive types of cancer 9,12‐15 . Perillyl alcohol can be converted to perillaldehyde and then to cumin aldehyde with the help of ecocatalyst 16 …”