Multiple sustainable methodologies were developed for the chemical upgrading of HMF: i) at 30-90 degrees C, highly selective base-catalyzed acetylation and carboxymethylation reactions of HMF with nontoxic reagents as isopropenyl acetate (iPAc) and dimethyl carbonate (DMC) were achieved to prepare the corresponding ester and carbonate products, (5-formylfuran-2-yl)methyl acetate (5-formylfuran-2-yl) methyl carbonate, respectively; ii) based on the combined use of iPAc/DMC with acetone, a tandem protocol of acetylation/transcarbonation and aldol condensation was designed to synthesize a variety of HMF-derived alpha,beta-unsaturated carbonyl compounds; iii) in water as a solvent, a chemoselective Pd-catalysed reductive amination of HMF with amino-alcohols also including glycerol derivatives, was developed using H-2 at atmospheric pressure; iv) finally, both HMF and its ester and carbonate products successfully underwent Wittig vinylation reactions promoted by a methyl carbonate phosphonium salt ([Ph3PCH3] [CH3OCO2]), to obtain the corresponding olefins. The vinylation reagent (the salt) was a DMC derivative. In all cases i-iv), not only processes occurred under mild conditions, but post-reaction procedures (work-up and purification) were optimized to isolate final products in high yields of 85-98%.

Diversified upgrading of HMF via green acetylation, aldol condensation, carboxymethylation, vinylation and reductive amination reactions

Davide Rigo;Daniele Polidoro;Alvise Perosa;Maurizio Selva
2021-01-01

Abstract

Multiple sustainable methodologies were developed for the chemical upgrading of HMF: i) at 30-90 degrees C, highly selective base-catalyzed acetylation and carboxymethylation reactions of HMF with nontoxic reagents as isopropenyl acetate (iPAc) and dimethyl carbonate (DMC) were achieved to prepare the corresponding ester and carbonate products, (5-formylfuran-2-yl)methyl acetate (5-formylfuran-2-yl) methyl carbonate, respectively; ii) based on the combined use of iPAc/DMC with acetone, a tandem protocol of acetylation/transcarbonation and aldol condensation was designed to synthesize a variety of HMF-derived alpha,beta-unsaturated carbonyl compounds; iii) in water as a solvent, a chemoselective Pd-catalysed reductive amination of HMF with amino-alcohols also including glycerol derivatives, was developed using H-2 at atmospheric pressure; iv) finally, both HMF and its ester and carbonate products successfully underwent Wittig vinylation reactions promoted by a methyl carbonate phosphonium salt ([Ph3PCH3] [CH3OCO2]), to obtain the corresponding olefins. The vinylation reagent (the salt) was a DMC derivative. In all cases i-iv), not only processes occurred under mild conditions, but post-reaction procedures (work-up and purification) were optimized to isolate final products in high yields of 85-98%.
2021
514
File in questo prodotto:
File Dimensione Formato  
MOLCAA-D-21-00664_Text_Rev14082021.pdf

Open Access dal 25/01/2023

Descrizione: articolo principale
Tipologia: Documento in Pre-print
Licenza: Creative commons
Dimensione 628.77 kB
Formato Adobe PDF
628.77 kB Adobe PDF Visualizza/Apri

I documenti in ARCA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10278/3750737
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 15
  • ???jsp.display-item.citation.isi??? 16
social impact