Chemo-enzymatic synthesis of a levoglucosenone-derived bi-functional monomer and its ring-opening metathesis polymerization in the green solvent Cyrene™

Fadlallah, Sami; Peru, Aurélien; Longe, Lionel; Allais, Florent

doi:10.1039/d0py01471k

Cited by 28 publications

(27 citation statements)

References 36 publications

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“…The few reports on the topic describe the synthesis of chiral epoxides as valuable precursors such as ethyl and methyl (S)‐3‐(oxiran‐2‐yl)propanoates ((S)‐1a/1b) 9 and the enzymatic reduction of levoglucosenone by an alkene reductase as a sustainable metal‐ and dihydrogen‐free access to Cyrene [70] . Moreover, Cyrene and its diols have only been recently employed as organic media in enzymatically syntheses of polyesters [23,73] …”

Section: Introductionmentioning

confidence: 99%

“…Cyrene is known to form a symmetrical aldol condensation product in the presence of a base, as well as being sensitive to strong acids, which limits its use in certain applications. [15] Cyrene has been explored as bio‐based solvent in wire coatings, [16] filtration membranes industry,[ 17 , 18 ] pharmaceuticals, [19] graphene dispersion, [20] cross‐coupling, [21] polymers,[ 22 , 23 ] MOFs syntheses, [24] solvent extraction [25] or drug delivery [26] where it has replaced toxic polar aprotic solvents such as dichloromethane (DCM), N ‐methyl‐2‐pyrrolidone (NMP), N , N ’‐dimethylformamide (DMF) or N , N ’‐dimethylacetamide (DMAc).…”

Section: Introductionmentioning

confidence: 99%

“… [70] Moreover, Cyrene and its diols have only been recently employed as organic media in enzymatically syntheses of polyesters. [ 23 , 73 ]…”

Section: Introductionmentioning

confidence: 99%

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Polymer Chemistry Applications of Cyrene and its Derivative Cygnet 0.0 as Safer Replacements for Polar Aprotic Solvents

et al. 2021

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This study explores a binary solvent system composed of biobased Cyrene and its derivative Cygnet 0.0 for application in membrane technology and in biocatalytic synthesis of polyesters. Cygnet‐Cyrene blends could represent viable replacements for toxic polar aprotic solvents. The use of a 50 wt % Cygnet‐Cyrene mixture makes a practical difference in the production of flat sheet membranes by nonsolvent‐induced phase separation. New polymeric membranes from cellulose acetate, polysulfone, and polyimide are manufactured by using Cyrene, Cygnet 0.0, and their blend. The resultant membranes have different morphology when the solvent/mixture and temperature of the casting solution change. Moreover, Cyrene, Cygnet 0.0, and Cygnet‐Cyrene are also explored for substituting diphenyl ether for the biocatalytic synthesis of polyesters. The results indicate that Cygnet 0.0 is a very promising candidate for the enzymatic synthesis of high molecular weight polyesters.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Polymer Chemistry Applications of Cyrene and its Derivative Cygnet 0.0 as Safer Replacements for Polar Aprotic Solvents

et al. 2021

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“…Given our strong expertise in levoglucosenone (LGO), a wood-based functional molecule produced at the scale of several tons per year [ 28 , 29 , 30 ], we have recently become interested in developing not only renewable functional monomers and polymers from LGO [ 31 , 32 , 33 , 34 , 35 , 36 ] but also biodegradation protocols to evaluate the end-of-life of our in-house corresponding materials. In this context, we recently reported the first fully renewable citronellol-containing monomers from LGO [ 34 , 35 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Enzymatic Degradation of Sustainable Levoglucosenone-Derived Copolyesters with Renewable Citronellol Side Chains

et al. 2022

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Recently, a renewable five-membered lactone containing citronellol (HBO-citro) was synthesized from levoglucosenone (LGO). A one-pot two-step pathway was then developed to produce a mixture of 5- and 6-membered Lactol-citro molecules (5ML and 6ML, respectively) from HBO-citro. Proton nuclear magnetic resonance (1H NMR) of a mixture of 5ML and 6ML at varying temperatures showed that the chemical shifts of the hydroxyls, as well as the 5ML:6ML ratio, are temperature-dependent. Indeed, a high temperature, such as 65 °C, led to an up-field shielding of the hydroxyl protons as well as a drop in the 5ML:6ML ratio. The monomers 5ML and 6ML were then engaged in polycondensation reactions involving diacyl chlorides. Renewable copolyesters with low glass transition temperatures (as low as −67 °C) and cross-linked citronellol chains were prepared. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan® 50 BG). A higher degradation rate was found for the polymers prepared using Lactol-citro molecules, compared to those obtained by the polycondensation reactions of diacyl chlorides with Triol-citro—a monomer recently obtained by the selective reduction of HBO-citro.

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“…A one-pot synthesis of HMF from cellulose via LGO is also possible, as discussed in a later section of this paper. , There have been studies on the production of functional polymers having unique structures of LGO or its derivative, ( S )-γ-hydroxymethyl-α,β-butenolide (HBO). A ring-opening metathesis polymerization of Diels–Alder adducts of LGO or HBO with cyclopentadiene produces polymers with a high thermal stability with a T d50% well-above 400 °C. − A high thermal stability is also found for polyesters produced from LGO-Cyrene diketone-derived bicyclic monomer, 2H-HBO-HBO, by polycondensation with diacyl chlorides …”

Section: Introductionmentioning

confidence: 99%

Catalytic Strategies for Levoglucosenone Production by Pyrolysis of Cellulose and Lignocellulosic Biomass

Kudo¹,

Huang

Asano³

et al. 2021

Energy Fuels

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Levoglucosenone (LGO) is a biobased compound that is generated during the pyrolysis of cellulose under catalysis. After several decades of foundational research into production methods, the relatively large-scale industrial production of LGO recently commenced. As a result, research on the application of LGO has increased and extended to the production of commodity chemicals, such as solvents, polymers, resins, and fuels, with LGO as the feedstock, while seeking to minimize production costs. An analysis and summary of previous achievements can help to inform the development of better production methods. We found that existing production methods can be organized into three categories depending on the strategies for exploiting catalysis. This minireview summarizes advances in the technologies used to produce LGO based on each catalytic strategy and recommends possible directions for future research by drawing on knowledge synthesized from the database.

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Chemo-enzymatic synthesis of a levoglucosenone-derived bi-functional monomer and its ring-opening metathesis polymerization in the green solvent Cyrene™

Abstract: The levoglucosenone-based norbornenes family was extended to include a new bi-functional methacrylate monomer that, upon ROMP in Cyrene™, leads to polymers with pendent methacrylate moieties which can be modified by post-polymerization reactions.

Cited by 28 publications

References 36 publications

Polymer Chemistry Applications of Cyrene and its Derivative Cygnet 0.0 as Safer Replacements for Polar Aprotic Solvents

Polymer Chemistry Applications of Cyrene and its Derivative Cygnet 0.0 as Safer Replacements for Polar Aprotic Solvents

Synthesis and Enzymatic Degradation of Sustainable Levoglucosenone-Derived Copolyesters with Renewable Citronellol Side Chains

Catalytic Strategies for Levoglucosenone Production by Pyrolysis of Cellulose and Lignocellulosic Biomass

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