Direct Conversion of Activated 5‐Hydroxymethylfurfural into δ‐Lactone‐Fused Cyclopentenones. Issue 2 (21st December 2018)

• Record Type: Journal Article
• Authors: Gomes, Rafael F. A.; Coelho, Jaime A. S.; Afonso, Carlos A. M.
• Is Part Of: ChemSusChem. Volume 12:Issue 2(2019)
• Page Start: 420
• Page End: 425
• Publication Date: 2018-12-21
• Subjects: biomass -- cyclization -- density functional calculations -- kinetics -- reaction mechanisms; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.201802537
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: Valorization of biomass derived feedstock (e.g., 5‐hydroxymethylfurfural platform) is a very active field of chemical research. In this study, 5‐hydroxymethylfurfural is converted into cyclopenten‐2‐ones by virtue of furfural's activation and Meldrum's acid's tendency to undergo decomposition/esterification. Experimental and computational studies suggest a domino rearrangement–lactonization reaction involving BINOL‐catalyzed lactonization as the rate‐determining step. The novel lactone‐fused cyclopenten‐2‐ones, which bear a quaternary carbon and resemble a didemnenone natural product structure, are converted into several derivatives with potential interest for the fields of synthetic and medicinal chemistry. Abstract : Meldrum‐atic : Several value‐added cyclopentenones bearing a quaternary carbon center were prepared from biomass‐derived 5‐hydroxymethylfurfural (HMF) by condensation with 2, 2‐dimethyl‐1, 3‐dioxane‐4, 6‐dione (Meldrum's acid) followed by a ring‐opening–cyclization–lactonization cascade process.