Eco‐Mn Ecocatalysts: Toolbox for Sustainable and Green Lewis Acid Catalysis and Oxidation Reactions

Bihanic, Camille; Richards, Kenza; Olszewski, Tomasz K.; Grison, Claude

doi:10.1002/cctc.201901845

Cited by 14 publications

(13 citation statements)

References 125 publications

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“…As has been done previously with G. gillivrayi [ 31 ], the Mn-rich biomasses of P. stratiotes could be transformed into three classes of ecocatalysts ( Figure 1 ). A first class of ecocatalysts was obtained by grinding the air-dried leaves or roots into a 1.5 mm powder, which was then heated to 550 °C, leading to formation of Eco-MnOx-Ps.…”

Section: Resultssupporting

confidence: 57%

“…The Grison group has shown that remediation phytotechnologies, such as phytoextraction [ 30 , 31 , 32 ], rhizofiltration [ 33 , 34 , 35 ] and biosorption [ 35 , 36 , 37 , 38 ], generate biomass rich in transition metals that can be turned into innovative catalysts, called ecocatalysts [ 39 , 40 , 41 ]. Using the concept of ecocatalysis, we advanced the aim that only natural or biosourced catalysts would be used for preparing the cyclic oxyterpenes.…”

Section: Introductionmentioning

confidence: 99%

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New Sustainable Synthetic Routes to Cyclic Oxyterpenes Using the Ecocatalyst Toolbox

et al. 2021

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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.

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Section: Resultssupporting

confidence: 57%

Section: Introductionmentioning

confidence: 99%

New Sustainable Synthetic Routes to Cyclic Oxyterpenes Using the Ecocatalyst Toolbox

et al. 2021

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“…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.…”

Section: Introductionmentioning

confidence: 99%

Green and Effective Preparation of α-Hydroxyphosphonates by Ecocatalysis

et al. 2022

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A green and effective approach for the synthesis of structurally diversed α-hydroxyphosphonates via hydrophosphonylation of aldehydes under solventless conditions and promoted by biosourced catalysts, called ecocatalysts “Eco-MgZnOx” is presented. Ecocatalysts were prepared from Zn-hyperaccumulating plant species Arabidopsis halleri, with simple and benign thermal treatment of leaves rich in Zn, and without any further chemical treatment. The elemental composition and structure of Eco-MgZnOx were characterized by MP–AES, XRPD, HRTEM, and STEM–EDX techniques. These analyses revealed a natural richness in two unusual and valuable mixed zinc–magnesium and iron–magnesium oxides. The ecocatalysts were employed in this study to demonstrate their potential use in hydrophosphonylation of aldehydes, leading to various α-hydroxyphosphonate derivatives, which are critical building blocks in the modern chemical industry. Computational chemistry was performed to help discriminate the role of some of the constituents of the mixed oxide ecocatalysts. High conversions, broad substrate scope, mild reaction conditions, and easy purification of the final products together with simplicity of the preparation of the ecocatalysts are the major advantages of the presented protocol. Additionally, Eco-MgZnOx-P could be recovered and reused for up to five times.

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“…In contrast, foliar Mn concentrations in Mn-hyperaccumulating species such as Grevillea meisneri can exceed 10,000 μg g −1 7 , 30 , 36 . Their Mn-rich biomass is easily valorized by the use of powdered leaves as green and highly efficient catalysts in organic chemistry 10 , 13 , 14 , 37 .…”

Section: Introductionmentioning

confidence: 99%

Manganese distribution in the Mn-hyperaccumulator Grevillea meisneri from New Caledonia

Bihanic

Petit

Perrot

et al. 2021

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New Caledonian endemic Mn-hyperaccumulator Grevillea meisneri is useful species for the preparation of ecocatalysts, which contain Mn–Ca oxides that are very difficult to synthesize under laboratory conditions. Mechanisms leading to their formation in the ecocatalysts are unknown. Comparing tissue-level microdistribution of these two elements could provide clues. We studied tissue-level distribution of Mn, Ca, and other elements in different tissues of G. meisneri using micro-X-Ray Fluorescence-spectroscopy (μXRF), and the speciation of Mn by micro-X-ray Absorption Near Edge Structure (µXANES), comparing nursery-grown plants transplanted into the site, and similar-sized plants growing naturally on the site. Mirroring patterns in other Grevillea species, Mn concentrations were highest in leaf epidermal tissues, in cortex and vascular tissues of stems and primary roots, and in phloem and pericycle–endodermis of parent cluster roots. Strong positive Mn/Ca correlations were observed in every tissue of G. meisneri where Mn was the most concentrated. Mn foliar speciation confirmed what was already reported for G. exul, with strong evidence for carboxylate counter-ions. The co-localization of Ca and Mn in the same tissues of G. meisneri might in some way facilitate the formation of mixed Ca–Mn oxides upon preparation of Eco-CaMnOx ecocatalysts from this plant. Grevillea meisneri has been successfully used in rehabilitation of degraded mining sites in New Caledonia, and in supplying biomass for production of ecocatalysts. We showed that transplanted nursery-grown seedlings accumulate as much Mn as do spontaneous plants, and sequester Mn in the same tissues, demonstrating the feasibility of large-scale transplantation programs for generating Mn-rich biomass.

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Eco‐Mn Ecocatalysts: Toolbox for Sustainable and Green Lewis Acid Catalysis and Oxidation Reactions

Cited by 14 publications

References 125 publications

New Sustainable Synthetic Routes to Cyclic Oxyterpenes Using the Ecocatalyst Toolbox

New Sustainable Synthetic Routes to Cyclic Oxyterpenes Using the Ecocatalyst Toolbox

Green and Effective Preparation of α-Hydroxyphosphonates by Ecocatalysis

Manganese distribution in the Mn-hyperaccumulator Grevillea meisneri from New Caledonia

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