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HMF in multicomponent reactions : Efficient routes towards novel fine chemicals

Abstract : Recently, the production of chemicals, either bulk or fine chemicals, from renewable biomass has attracted growing interests due to the dwindling reserve of fossil resources and the increasing awareness of environmental concerns. Some chemicals with a structure able to generate a number of derivatives, and able to be directly produced from biomass, are referred to as bio-based “platform chemicals”, and constitute the bridge between biomass and down-stream chemicals. Among these chemicals, 5-hydroxymethylfurfural (HMF), bearing an aldehyde group, a hydroxymethyl group, and a furan moiety, is the most popular one. However, its limited stability obstructs its applications in organic synthesis. Thus, developing mild and efficient synthetic routes towards existing or novel fine chemicals from HMF is still a challenging task. Multicomponent reactions (MCRs) are powerful synthetic tools allowing the straightforward formation of elaborated molecules from simple starting materials in a time- and step-saving manner. Among MCRs, many involve the aldehyde as one of the reactive components, making HMF as a potential interesting substrate in such strategies. This thesis aims at exploring the use of HMF in MCRs to provide novel fine chemicals, focusing on two reactions, namely the Biginelli and Kabachnik-Fields reactions. The Biginelli reaction is a condensation of an aldehyde, a dicarbonyl compound and urea. Although it is an old reaction, it is still showing thriving vitality, as many of its products, namely dihydropyrimidinones, exhibit various biological properties. We have investigated the reaction by choosing proper conditions to adapt to HMF, notably with respect to acidic conditions. The best conditions found for the reaction are the use of ZnCl2 as a mild Lewis acid catalyst without any solvent, giving access to new dihydropyrimidinones in modest to good yields. The Kabachnik-Fields reaction is a one-pot condensation of aldehydes, amines and dialkyl phosphites, and is considered as the most efficient and convenient approach to a-aminophosphonates. For the specific case of HMF, we could establish that the best conditions were the use of iodine as a catalyst in the bio-based solvent 2-MeTHF and room or moderately elevated temperature. Using these optimized conditions, a wide range of HMF-based a-aminophosphonates were prepared in modest to excellent yields. The hydroxymethyl group persisting in HMF-based a-aminophosphonates offers the possibilities of further modification and derivatization, illustrating the benefit of HMF as compared to furfural, for accessing a wider scope of chemical structures.
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Submitted on : Tuesday, December 10, 2019 - 4:23:30 PM
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Weigang Fan. HMF in multicomponent reactions : Efficient routes towards novel fine chemicals. Theoretical and/or physical chemistry. Université de Lyon, 2019. English. ⟨NNT : 2019LYSEI022⟩. ⟨tel-02402915⟩

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