The Increasing Value of Biomass: Moving From C6 Carbohydrates to Multifunctionalized Building Blocks via 5‐(hydroxymethyl)furfural

Abstract

Recent decades have been marked by enormous progress in the field of synthesis and chemistry of 5‐(hydroxymethyl)furfural (HMF), an important platform chemical widely recognized as the “sleeping giant” of sustainable chemistry. This multifunctional furanic compound is viewed as a strong link for the transition from the current fossil‐based industry to a sustainable one. However, the low chemical stability of HMF significantly undermines its synthetic potential. A possible solution to this problem is synthetic diversification of HMF by modifying it into more stable multifunctional building blocks for further synthetic purposes.

Homogeneous Catalyzed Valorization of Furanics: A Sustainable Bridge to Fuels and Chemicals

“…For example, the typical reactions that the furanic aldehyde functionality can undergo are reduction to alcohols by H 2 or by hydrogen transfer (Meerwein-Ponndorf-Verley reduction) [47], decarbonylation [48], reductive amination to amines [49], oxidation to carboxylic acid [50], acetalization [51], aldol and Knoevenagel condensations [52], acylation, and Grignard reactions [53]. The second reactive functionality is the hydroxyl group that can undergo hydrogenolysis of the C−O bond, oxidation to an aldehyde or acid, etherification, acetalization, esterification, and halogenation reactions [54]. The catalytic deoxygenation of biomass is very important to produce highly functional intermediates, such as furanics with aldehyde and alcohol moieties [46].…”

Diels–Alder Cycloadditions of Bio-Derived Furans with Maleimides as a Sustainable «Click» Approach towards Molecular, Macromolecular and Hybrid Systems

“…However, a high exo-diastereoselectivity for N-phenyl maleimide was reached by conduction of the DA reaction with FA under solvent-free conditions at high temperatures (Table 2 1 Yield of crude product. 2 One-pot DA/hydrogenation on Pd/C. 3 Determined by NMR.…”

“…Chemical modification of biomass-derived furanic platform chemicals furfural (FF) and 5-(hydroxymethyl)furfural (HMF) is a growing area of sustainable chemistry that is considered one of the general approaches for the replacement of traditional oil-based chemical production by biorefining based on renewable resources [1][2][3][4][5]. The major synthetic transformations of renewable furans are focused on the production of biofuels, chemicals and materials, in accordance with the sustainability concept [6][7][8][9][10][11].…”

Intermolecular Diels-Alder Cycloadditions of Furfural-Based Chemicals from Renewable Resources: A Focus on the Regio- and Diastereoselectivity in the Reaction with Alkenes

“…As expected, the key role of biobased technologies is to replace the key existing products of oil-based refinement with renewables [ 4 , 6 , 7 ]. The tremendous synthetic potential explains the unprecedented scale of research in the fields of synthesis and application of furanic platform chemicals for the production of biofuels, chemicals, polymers and other industrially important products, which was evidenced by the increasing number of relevant publications (partially since 2010, Figure 1 ) and was highlighted in many recent reviews [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 ].…”