Recent Advances on Diels‐Alder‐Driven Preparation of Bio‐Based Aromatics

Abstract

The preparation of high value‐added chemicals from renewable resources is a crucial approach towards a sustainable economy. One prominent alternative to the production of petroleum‐based chemicals from fossil resources is through the sequential Diels‐Alder/aromatization reactions of biomass‐derived furan platforms. This Concept is focused on the recent boom in bio‐based furan DA strategies for aromatization of bio‐based platform chemicals, particularly that of furfurals, ranging from indirect use and activation strategies to recent examples of direct DA reaction of these electron‐withdrawing biomass‐derived furans.

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

“…The dehydration of furan/alkene adducts is an important sustainable approach to accessing renewable aromatic chemicals ( Scheme 6 ) [ 7 , 30 , 37 , 115 , 116 , 117 ]. Utilization of HMF-derived C6 renewable furans (especially 2,5-dimethylfuran or 2,5-furandicarboxylic acid) provides access to para -substituted aromatics (as a route towards “green” polymers) and various polysubstituted aromatic products ( Scheme 6 ) [ 116 ].…”

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

“…The general routes of applications include the synthesis of aliphatic or aromatic cyclic products, biologically active compounds, monomers and polyfunctional scaffolds. Reductions in the double bond in the furan-derived oxanorbornenes is a route to oxanorbornanes, structural analogs of the bioactive small molecules cantharidin (natural terpenoid isolated from Spanish fly blister beetles) and its synthetic analogs norcantharidin and norcantharimides, which Several recent reviews covered the scientific literature regarding the development of functional or dynamic macromolecular systems employing the fmDA approach [19][20][21]; other reviews provided detailed information about the reactivity of biobased furans in DA cycloadditions [16,22,23]; however, in the context of fmDA reactions, these coverages are not comprehensive or need updating. In this review, we briefly survey recent research trends in the application of the furan/maleimide-based «click» methodology for the production of functional or dynamic molecular, biomolecular and macromolecular systems.…”

“…They found a significant increase in the efficiency of the DA reaction of maleimides with furanic aldehydes, furoic A high level of progress was recently achieved for DA reactions with low reactive acceptor-substituted furans by Bruijnincx and co-workers. They found a significant increase in the efficiency of the DA reaction of maleimides with furanic aldehydes, furoic Acid-or base-catalyzed dehydration of the furan-derived oxanorbornenes is an important approach to access a renewable aromatics [15,22,23]. In the case of furan-maleimidederived oxanorbornenes, this reaction led to the formation of renewable phtalimides (Scheme 1).…”

“…Due to its high efficiency, excellent selectivity, 100% atom economy and the biobased nature of most of the furanic substrates, the fmDA reaction may be considered as a sustainable «click» approach for the production of functional or dynamic molecular, biomolecular and macromolecular systems (Figure 1). Several recent reviews covered the scientific literature regarding the development of functional or dynamic macromolecular systems employing the fmDA approach [19][20][21]; other reviews provided detailed information about the reactivity of biobased furans in DA cycloadditions [16,22,23]; however, in the context of fmDA reactions, these coverages are not comprehensive or need updating. In this review, we briefly survey recent research trends in the application of the furan/maleimide-based «click» methodology for the production of functional or dynamic molecular, biomolecular and macromolecular systems.…”

Production of Copolyester Monomers from Plant‐Based Acrylate and Acetaldehyde

“…[3] An attractive avenue relies on the valorization of platform molecules which can be easily obtained via biomass refinery. [4] For example, the conversion of plant-based furan derivatives into arenes, [5] aromatic acids, [6] nitrogen compounds, [7] and polymers [8] has been extensively investigated over the past decades. In comparison, less attention has been paid to other platform compounds.…”