Exploration of benign deep eutectic solvent–water systems for the highly efficient production of furfurylamine from sugarcane bagasse <i>via</i> chemoenzymatic cascade catalysis

Li, Qing; Di, Junhua; Liao, Xiaolong; Ni, Jiacheng; Li, Qi; He, Yiming; Ma, Cuiluan

doi:10.1039/d1gc03010h

Cited by 58 publications

(44 citation statements)

References 67 publications

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“…In recent times, efforts have been intensified toward the valorization of biomass derivatives as a strategy to promote sustainable chemical synthesis. 64 Conversion of biomass-derived starting materials to amines has only recently received attention, 61 , 65 − 67 and bioconversion methods have largely focused on the amination of biomass-derived aldehydes/ketones to generate primary amines. 61 , 67 Secondary and tertiary amines are frequently encountered as structural components in numerous bioactive compounds ( e.g ., pharmaceuticals, agrochemicals, and natural products).…”

Section: Resultsmentioning

confidence: 99%

Enzymatic N-Allylation of Primary and Secondary Amines Using Renewable Cinnamic Acids Enabled by Bacterial Reductive Aminases

Aleku

Titchiner

Roberts

et al. 2022

ACS Sustainable Chem. Eng.

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Allylic amines are a versatile class of synthetic precursors of many valuable nitrogen-containing organic compounds, including pharmaceuticals. Enzymatic allylic amination methods provide a sustainable route to these compounds but are often restricted to allylic primary amines. We report a biocatalytic system for the reductive N -allylation of primary and secondary amines, using biomass-derivable cinnamic acids. The two-step one-pot system comprises an initial carboxylate reduction step catalyzed by a carboxylic acid reductase to generate the corresponding α,β-unsaturated aldehyde in situ . This is followed by reductive amination of the aldehyde catalyzed by a bacterial reductive aminase pIR23 or BacRedAm to yield the corresponding allylic amine. We exploited pIR23, a prototype bacterial reductive aminase, self-sufficient in catalyzing formal reductive amination of α,β-unsaturated aldehydes with various amines, generating a broad range of secondary and tertiary amines accessed in up to 94% conversion under mild reaction conditions. Analysis of products isolated from preparative reactions demonstrated that only selective hydrogenation of the C=N bond had occurred, preserving the adjacent alkene moiety. This process represents an environmentally benign and sustainable approach for the synthesis of secondary and tertiary allylic amine frameworks, using renewable allylating reagents and avoiding harsh reaction conditions. The selectivity of the system ensures that bis-allylation of the alkylamines and (over)reduction of the alkene moiety are avoided.

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Section: Resultsmentioning

confidence: 99%

Enzymatic N-Allylation of Primary and Secondary Amines Using Renewable Cinnamic Acids Enabled by Bacterial Reductive Aminases

Aleku

Titchiner

Roberts

et al. 2022

ACS Sustainable Chem. Eng.

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“…The reason may be because NH4 + is a kind of Bronsted acid, which could catalyze NAG into 3A5AF. Meanwhile, Cl − had the ability to stabilize the structure of transition‐state and prevent undesired side‐reaction, which led to an increase in 3A5AF production [19] . Thus, NH 4 Cl was chosen as the catalyst in the following experiment.…”

Section: Resultsmentioning

confidence: 99%

Conversion of N‐Acetyl‐D‐glucosamine into 3‐Acetamido‐5‐acetylfuran Using Cheap Ammonium Chloride as Catalyst

Wang

Zhang

et al. 2022

ChemistrySelect

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Herein, we propose a facile method for converting N‐acetyl‐D‐glucosamine (NAG) into the N‐containing chemical 3‐acetamido‐5‐acetylfuran (3A5AF) using chloride salt as a catalyst. Screening of various chloride salts showed that NH4Cl possessed the optimal catalytic performance. The catalyst NH4Cl led to a 3A5AF yield of 43 mol % with LiCl as an additive in N,N‐dimethylformamide (DMF) solvent at 160 °C for 5 min. Moreover, the solvent, catalyst and additive could be reused at least five times with residual catalytic activity of 94.42 %. Additionally, scaling up of the 3A5AF preparation could be easily realized and the purity of the product 3A5AF reached >99 % purity with 45 mol % isolated yield after a simple isolation procedure. This work provides an environmentally friendly and mild method for converting NAG into 3A5AF.

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“…Lewis and Brønsted acid sites can isomerize aldose-ketose and accelerate furfural formation via ring dehydration ( Li et al, 2022 ). Li et al creatively used spent shrimp shells as a starting material to prepare sulfonated tin-based solid acids (Sn-SS) for the conversion of sugarcane bagasse (SB) to furfural in DES (ChCl/EG)-water at 170°C for 20 min, yielding 62.3% furfural ( Table 5 , entry 4) ( Li et al, 2021a ). The hydrogen bonds in SB were broken by ChCl/EG, and the Sn-SS solid acid could pretreat and depolymerize SB.…”

Section: Catalytic Conversion Of Biomass To Furfural In Deep Eutectic...mentioning

confidence: 99%

Recent Advances in the Catalytic Conversion of Biomass to Furfural in Deep Eutectic Solvents

Zhang

Zhu

et al. 2022

Front. Chem.

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Lignocellulose is recognized as an ideal raw material for biorefinery as it may be converted into biofuels and value-added products through a series of chemical routes. Furfural, a bio-based platform chemical generated from lignocellulosic biomass, has been identified as a very versatile alternative to fossil fuels. Deep eutectic solvents (DES) are new “green” solvents, which have been employed as green and cheap alternatives to traditional organic solvents and ionic liquids (ILs), with the advantages of low cost, low toxicity, and biodegradability, and also have been proven to be effective media for the synthesis of biomass-derived chemicals. This review summarizes the recent advances in the conversion of carbohydrates to furfural in DES solvent systems, which mainly focus on the effect of adding different catalysts to the DES system, including metal halides, water, solid acid catalyst, and certain oxides, on the production of furfural. Moreover, the challenges and perspectives of DES-assisted furfural synthesis in biorefinery systems are also discussed in this review.

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Exploration of benign deep eutectic solvent–water systems for the highly efficient production of furfurylamine from sugarcane bagasse via chemoenzymatic cascade catalysis

Abstract: Recently, cost-effective production of highly value-added furan chemicals from abundant and renewable bioresources has gained much attentions via chemoenzymatic approach in environmentally-friendly reaction system. In this work, chemoenzymatic cascade reaction...

Cited by 58 publications

References 67 publications

Enzymatic N-Allylation of Primary and Secondary Amines Using Renewable Cinnamic Acids Enabled by Bacterial Reductive Aminases

Enzymatic N-Allylation of Primary and Secondary Amines Using Renewable Cinnamic Acids Enabled by Bacterial Reductive Aminases

Conversion of N‐Acetyl‐D‐glucosamine into 3‐Acetamido‐5‐acetylfuran Using Cheap Ammonium Chloride as Catalyst

Recent Advances in the Catalytic Conversion of Biomass to Furfural in Deep Eutectic Solvents

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