The Lord of the Chemical Rings: Catalytic Synthesis of Important Industrial Epoxide Compounds

Meng, Yudong; Taddeo, Francesco; Aguilera, Adriana Freites; Cai, Xiaoshuang; Russo, Vincenzo; Tolvanen, Pasi; Leveneur, Sébastien

doi:10.3390/catal11070765

Cited by 46 publications

(38 citation statements)

References 140 publications

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“…Recent advances in catalysis could help circumventing these issues and render epoxide syntheses greener. [102][103][104][105][106] Alternatively, transesterification-based vitrimers could be synthesized via epoxide-free route. For instance, ester and hydroxyl containing biosourced monomers could be cross-linked by free radical polymerization of C═C unsaturation, another common chemical function in biobased precursors.…”

Section: Discussionmentioning

confidence: 99%

Fully Biobased Vitrimers: Future Direction toward Sustainable Cross‐Linked Polymers

Vidil

Llevot

2022

Macro Chemistry & Physics

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Improving the sustainability of polymer networks is a crucial challenge in polymer science due to their important role in industry. Their traditional syntheses conflict with several principles of green chemistry as the employed monomers are petroleum-based, their production involves the use of toxic reagents, and their permanently cross-linked structures impede their chemical recycling and reshaping. The development of vitrimers represents a unique solution to address the issue of polymer network end-of-life by enabling reprocessability while maintaining good thermomechanical properties and solvent resistance. Although over the last decades biomass has proved to be an excellent feedstock for the production of permanently cross-linked polymers, the field of biobased vitrimers is still in its infancy. In this review, a comprehensive overview of vitrimers synthesized from biobased monomers is presented. The emphasis is set on the compatibility of the biomass structure with the nature of the dynamic covalent chemistry, as well as the sustainability of the synthetic approaches. Implementing renewable feedstocks and recyclability in the production of polymer networks paves the way for the development of the next generation of sustainable materials.

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Section: Discussionmentioning

confidence: 99%

Fully Biobased Vitrimers: Future Direction toward Sustainable Cross‐Linked Polymers

Vidil

Llevot

2022

Macro Chemistry & Physics

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“…Besides transesterification, epoxidation is one of the most widely applied chemical modifications of vegetable oils. Despite the availability of several efficient methodologies to synthesize epoxidized vegetable oils, the Prilezhaev reaction is probably the most widely employed methodology, mostly at the industrial level [35][36][37]. The overall reaction is a two-step process occurring in a biphasic system, as diagrammatically shown in Scheme 4.…”

Section: Introductionmentioning

confidence: 99%

Recovery, Purification, Analysis and Chemical Modification of a Waste Cooking Oil

Azzena

Montenero²,

Carraro

et al. 2022

Waste Biomass Valor

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Disposing of residual cooking oil is a major environmental concern, so its conversion into commercial products is a desirable goal. To design the chemical modification of a domestic waste oil into valuable biochemicals other than biodiesel, we analyzed a series of its samples, collected over a period of three years, using quantitative 1H-NMR. This analysis, allowing a quick determination of its main chemical characteristics, has rendered the image of a vegetable oil with an almost constant composition over time and with a relative low content of saturated fatty acids. To make this collection protocol more economical, we projected its chemical transformation into esters and epoxidized esters of long chain and branched alcohols, which could find employment as biolubricants and/or bioplasticizers. The one-pot transesterification of the waste cooking oil into esters of commercially available and biodegradable Guerbet alcohols was obtained under environmentally friendly conditions by employing commercial CaO as a catalyst. Additionally, microwave irradiation of this reaction allowed to optimize the energy expenditure by significantly reducing the reaction time as compared with reactions run under conventional heating. To improve their oxidation stabilities, the resulting esters were epoxidized under conditions useful to minimize side-reactions. An investigation of their main rheological properties shows that some of the resulting products display characteristics that make their use as biolubricants or bioplasticizers predictable. The entire process represents a virtuous example of circular economy. Graphical Abstract

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“…The oxirane ring of epoxides has been termed the "lord of the chemical rings" due to reactivity and relevance in different organic syntheses of industrial importance [54]. In the present study, the selective epoxidation of long-chain terminal alkenes by several UPOs from the basidiomycetous fungi A. aegerita, C. cinerea, and M. rotula; and the ascomycetous species C. globosum, H. insolens, and D. caldariorum was investigated (using GC-MS analysis).…”

Section: Resultsmentioning

confidence: 99%

Enzymatic Epoxidation of Long-Chain Terminal Alkenes by Fungal Peroxygenases

et al. 2022

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Terminal alkenes are among the most attractive starting materials for the synthesis of epoxides, which are essential and versatile intermediate building blocks for the pharmaceutical, flavoring, and polymer industries. Previous research on alkene epoxidation has focused on the use of several oxidizing agents and/or different enzymes, including cytochrome P450 monooxygenases, as well as microbial whole-cell catalysts that have several drawbacks. Alternatively, we explored the ability of unspecific peroxygenases (UPOs) to selectively epoxidize terminal alkenes. UPOs are attractive biocatalysts because they are robust extracellular enzymes and only require H2O2 as cosubstrate. Here, we show how several UPOs, such as those from Cyclocybe (Agrocybe) aegerita (AaeUPO), Marasmius rotula (MroUPO), Coprinopsis cinerea (rCciUPO), Humicola insolens (rHinUPO), and Daldinia caldariorum (rDcaUPO), are able to catalyze the epoxidation of long-chain terminal alkenes (from C12:1 to C20:1) after an initial optimization of several reaction parameters (cosolvent, cosubstrate, and pH). In addition to terminal epoxides, alkenols and other hydroxylated derivatives of the alkenes were formed. Although all UPOs were able to convert and epoxidize the alkenes, notable differences were observed between them, with rCciUPO being responsible for the highest substrate turnover and MroUPO being the most selective with respect to terminal epoxidation. The potential of peroxygenases for epoxidizing long-chain terminal alkenes represents an interesting and green alternative to the existing synthesis technologies.

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The Lord of the Chemical Rings: Catalytic Synthesis of Important Industrial Epoxide Compounds

Cited by 46 publications

References 140 publications

Fully Biobased Vitrimers: Future Direction toward Sustainable Cross‐Linked Polymers

Fully Biobased Vitrimers: Future Direction toward Sustainable Cross‐Linked Polymers

Recovery, Purification, Analysis and Chemical Modification of a Waste Cooking Oil

Enzymatic Epoxidation of Long-Chain Terminal Alkenes by Fungal Peroxygenases

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