Review article
Furfural and 5-(hydroxymethyl)furfural: Two pivotal intermediates for bio-based chemistry

https://doi.org/10.1016/j.cogsc.2020.100384Get rights and content

Highlights

  • Furfural and 5-(hydroxymethyl)furfural offer rare opportunities for designing novel biobased products and will play a central role in tomorrow's chemistry.

  • The renewability benefit should not be overstated as it is only a part of the cumulative ‘carbon cost’ of the derived chemicals.

  • Progresses result from subtle combinations of catalyst design, solvent and process optimization, mechanistic studies, and the use of cruder, cheaper raw material.

  • Explorative synthetic chemistry using furfural and hydroxymethylfurfural must be developed for discovering new architectures.

  • Original molecular designs will offer possible novel applicative properties and improved environmental impact.

Research on furfural and 5-(hydroxymethyl)furfural concerns all fields of chemistry: catalysis, mechanistic studies, synthetic organic chemistry, materials sciences, and chemical engineering. The purpose of this account is, by picking a selection of the very recent literature, to show the vitality of the field and to illustrate how transdisciplinary approaches can help overcoming the strong overlap between catalysts, solvent, and process issues. It highlights the necessity to encourage researches in two main directions, one being the optimization of the access to industrially relevant targets and the second being the commitment of synthetic organic chemists to explorative studies on new reactions and new architectures.

Introduction

A new chemical tree from C5–C6 carbohydrates via furfural and 5-(hydroxymethyl)furfural (HMF) is now established. These two furanic aldehydes offer rare opportunities for designing novel bio-based products exhibiting promising applications as commodities or specialty chemicals including monomers, solvents, fuels, and fine chemicals [1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14].

Although renewability is an important point, its beneficial contribution (renewable versus fossil) to the overall product’s carbon footprint should not be overstated. All other contributions (reagents, catalysts, solvents, heat, separation, utilization of the product and its end of life) account indeed, to the major part of the cumulative ‘carbon cost’. This is why, in keeping with the modern vision of green chemistry and engineering [15], the topic must be considered globally and address all issues, including cheaper and more sustainable raw materials, safer and cleaner processes, and diversification in molecular design of the derivatives.

The difficulty lies on the overlap between several key fundamental issues: adapting the catalyst to different starting resources, finding appropriate ‘catalyst/solvent’ couples with higher ‘dehydration–isolation’ efficiency, or looking for more selective and efficient subsequent transformations. In all of these directions, innovation results from a subtle combination of catalyst design, solvent and process optimization, and mechanistic considerations. Overall, several facets of green chemistry subtly overlap, such as catalyst design, use of non-edible biomass, clean solvent and processes, molecular design, selectivity, making this topic a fascinating school case (Figure 1).

This short opinion account aims at highlighting first the variety of approaches by picking a selection of very recent papers exemplifying the ‘resource–catalyst–solvent’ triple challenge of furfural and HMF synthesis. Next, among applications and uses, a focus is made on furfural-derived bio-based solvents and on HMF oxidations and reductions toward monomers. A short section also covers the bridge between C5–C6 chemistries. This account gives the viewpoint of synthetic organic chemists, stressing the benefits of the progress in the design of catalysts and processes and encouraging further synthetic exploration for diversifying the realm of possible products and applications.

Section snippets

Synthesis

Xylose is the substrate of choice for the synthesis of furfural. However, there are still some limitations to the efficacy of its dehydration to furfural, with selectivity issues due to the formation of humins necessitating to start from low xylose concentrations. Recent investigations have focused on the exploration of different catalysts, various media, and possible activation by additives.

Chatterjee et al. [16] reported that activated coal fly ash at 170 °C allowed achieving 85% conversion

Synthesis

HMF is the acid-catalyzed triply dehydrated product of C6 carbohydrates. In this reaction, the key issues are the selectivity, because of the limited stability of HMF in acidic conditions, and the possible use of hexose-containing starting materials cheaper than the very reactive fructose. Many studies reported recently (Table 1) have addressed both issues, by proposing specifically designed catalysts and solvents.

Reactivity of HMF

The recent literature on HMF-derived products is extremely rich and diversified

Bridging the C5 and C6 branches of the furfural/HMF chemical tree

Adding a carbon atom (+C1) to furfural or removing a carbon atom from HMF (−C1) is also an interesting strategy to switch from C5 to C6 sugars or vice versa. This may be related to price and availability issues, as furfural is still significantly cheaper and more abundant than HMF. It may also be appealing in terms of reactivity, when one useful C5 target can be obtained more easily or only from HMF. In the following passages, two examples illustrate the ±C1 options.

Carbonylation of furfural to

Conclusions

The vitality of the chemistry of C5 and C6 sugars is so high that furfural and HMF will very likely play a central role in tomorrow's chemistry, benefiting from efforts of chemists in all disciplines, from theoretical to engineering via synthesis and catalysis. Although the ‘furfural tree’ is rather mature already, the HMF one is still incomplete. Apart from the need to widen the range of resources to raw biomass that should replace refined sugars to improve the economic viability of the

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

The authors thank the Ministère de l’Enseignement Supérieur, de la Recherche et de l’Innovation (MESRI) and CNRS for their financial support, as well as the Chinese Scholarship Council (Université de Lyon-CSC call) for the fellowship to GS.

References (141)

  • C.B.T.L. Lee et al.

    One-pot furfural production using choline chloride-dicarboxylic acid based deep eutectic solvents under mild conditions

    Bioresour Technol

    (2019)
  • C.A. Bizzi et al.

    Furfural production from lignocellulosic biomass by ultrasound-assisted acid hydrolysis

    Ultrason Sonochem

    (2019)
  • A. Dunbabin et al.

    Furfurylamines from biomass: transaminase catalyzed upgrading of furfurals

    Green Chem

    (2017)
  • S. Jiang et al.

    Conversion of furfural to tetrahydrofuran-derived secondary amines under mild conditions

    Green Chem

    (2020)
  • X. Huang et al.

    Clean synthesis of 5-hydroxymethylfurfural and levulinic acid by aqueous phase conversion of levoglucosenone over solid acid catalysts

    ACS Sustainable Chem Eng

    (2019)
  • S. Marullo et al.

    Activity of a heterogeneous catalyst in deep eutectic solvents: the case of carbohydrate conversion into 5-hydroxymethylfurfural

    ACS Sustainable Chem Eng

    (2019)
  • S. Xu et al.

    Efficient conversion of glucose into 5-hydroxymethylfurfural using a bifunctional Fe3+ modified Amberlyst-15 catalyst

    Sustainable Energy Fuels

    (2019)
  • R.J.J. Ganado et al.

    Microwave-assisted conversion of simple sugars and waste coffee grounds into 5-hydroxymethylfurfural in a highly aqueous DMSO solvent system catalyzed by a combination of Al(NO3)3 and H2SO4

    Ind Eng Chem Res

    (2019)
  • J. Cao et al.

    Highly effective transformation of carbohydrates to 5-Hydroxymethylfurfural with Al-montmorillonite as catalyst

    Appl Catal A

    (2019)
  • X. Li et al.

    Dehydration of fructose, sucrose and inulin to 5-hydroxymethylfurfural over yeast-derived carbonaceous microspheres at low temperatures

    RSC Adv

    (2019)
  • A. Mukherjee et al.

    Production of 5-hydroxymethylfurfural from starch through an environmentally-friendly synthesis pathway

    Catal Lett

    (2019)
  • R.F.A. Gomes et al.

    Going beyond the Limits of the biorenewable platform: sodium dithionite-promoted stabilization of 5-hydroxymethylfurfural

    ChemSusChem

    (2018)
  • L. Chen et al.

    MnOx/P25 with tuned surface structures of anatase-rutile phase for aerobic oxidation of 5-hydroxymethylfurfural into 2, 5-diformylfuran

    Catal Today

    (2019)
  • J. Liu et al.

    Electrochemical oxidation of 5-Hydroxymethylfurfural with NiFe layered double hydroxide (LDH) nanosheet catalysts

    ACS Catal

    (2018)
  • P. Zhang et al.

    Paired electrocatalytic oxygenation and hydrogenation of organic substrates with water as the oxygen and hydrogen source

    Angew Chem Int Ed

    (2019)
  • G.W. Huber et al.

    Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering

    Chem Rev

    (2006)
  • R. Mariscal et al.

    Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels

    Energ Environ Sci

    (2016)
  • Y. Lee et al.

    Polymers derived from hemicellulosic parts of lignocellulosic biomass

    Rev Environ Sci Biotechnol

    (2019)
  • M.J. Climent et al.

    Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels

    Green Chem

    (2014)
  • A. Mittal et al.

    Production of furfural from process-relevant biomass-derived pentoses in a biphasic reaction system

    ACS Sustainable Chem Eng

    (2017)
  • A.A. Rosatella et al.

    5-Hydroxymethylfurfural (HMF) as a building block platform: biological properties, synthesis and synthetic applications

    Green Chem

    (2011)
  • R.J. van Putten et al.

    Hydroxymethylfurfural, a versatile platform chemical made from renewable resources

    Chem Rev

    (2013)
  • F.A. Kucherov et al.

    Chemical transformations of biomass-derived C6-furanic platform chemicals for sustainable energy research, materials science, and synthetic building blocks

    ACS Sustainable Chem Eng

    (2018)
  • A. Farrán et al.

    Green solvents in carbohydrate chemistry: from raw materials to fine chemicals

    Chem Rev

    (2015)
  • H. Li et al.

    Carbon-increasing catalytic strategies for upgrading biomass into energy-intensive fuels and chemicals

    ACS Catal

    (2018)
  • M.J. Hülsey et al.

    Sustainable routes for the synthesis of renewable heteroatom-containing chemicals

    ACS Sustainable Chem Eng

    (2018)
  • P.T. Anastas et al.

    The periodic table of the elements of green and sustainable chemistry

    Green Chem

    (2019)
  • A. Chatterjee et al.

    Modified coal fly ash waste as an efficient heterogeneous catalyst for dehydration of xylose to furfural in biphasic medium

    Fuel

    (2019)
  • Q. Wang et al.

    Production of furfural with high yields from corncob under extremely low water/solid ratios

    Renew Energy

    (2019)
  • L. Zhang et al.

    Transformation of corncob into furfural by a bifunctional solid acid catalyst

    Bioresour Technol

    (2019)
  • S. Jiang et al.

    Unveiling the role of choline chloride in furfural synthesis from highly concentrated feeds of xylose

    Green Chem

    (2018)
  • Z. Chen et al.

    One-pot selective conversion of lignocellulosic biomass into furfural and Co-products using aqueous choline chloride/methyl isobutyl ketone biphasic solvent system

    Bioresour Technol

    (2019)
  • Y. Zhao et al.

    Enhanced furfural production from biomass and its derived carbohydrates in the renewable butanone-water solvent system

    Sustainable Energy Fuels

    (2019)
  • T. Yang et al.

    Insight into aluminum sulfate-catalyzed xylan conversion into furfural in a γ-valerolactone/water biphasic solvent under microwave conditions

    ChemSusChem

    (2017)
  • B. Seemala et al.

    Levulinic acid as a catalyst for the production of 5-hydroxymethylfurfural and furfural from lignocellulose biomass

    ChemCatChem

    (2016)
  • M. Chatterjee et al.

    Reductive amination of furfural to furfurylamine using aqueous ammonia solution and molecular hydrogen: an environmentally friendly approach

    Green Chem

    (2016)
  • Z. Yuan et al.

    Preparation of nitrogen-doped carbon supported cobalt catalysts and its application in the reductive amination

    J Catal

    (2019)
  • I. Scodeller et al.

    Synthesis of renewable meta-xylylenediamine from biomass-derived furfural

    Angew Chem Int Ed

    (2018)
  • S. Jiang et al.

    Selective synthesis of THF-derived amines from biomass-derived carbonyl compounds

    ACS Catal

    (2019)
  • L. Kipshagen et al.

    Anionic surfactants based on intermediates of carbohydrate conversion

    Green Chem

    (2019)
  • Cited by (0)

    View full text