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.
Keywords: biomass; cyclization; density functional calculations; kinetics; reaction mechanisms.
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