Cascade Synthesis of Five-Membered Lactones using Biomass-Derived Sugars as Carbon Nucleophiles
Sho Yamaguchi1, Takeaki Matsuo2, Ken Motokura2
1Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-14 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa, 226-8502, Japan. syamaguchi@chemenv.titech.ac.jp.
Abstract:
We report the cascade synthesis of five-membered lactones from a biomass-derived triose sugar, 1,3-dihydroxyacetone, and various aldehydes. This achievement provides a new synthetic strategy to generate a wide range of valuable compounds from a single biomass-derived sugar. Among several examined Lewis acid catalysts, homogeneous tin chloride catalysts exhibited the best performance to form carbon-carbon bonds. The scope and limitations of the synthesis of five-membered lactones using aldehyde compounds are investigated. The cascade reaction led to high product selectivity as well as diastereoselectivity, and the mechanism leading to the diastereoselectivity was discussed based on isomerization experiments and density functional theory (DFT) calculations. The present results are expected to support new approaches for the efficient utilization of biomass-derived sugars.
Related Concept Videos
Ketones with Nonenolizable Aromatic Aldehydes: Claisen–Schmidt Condensation
As the self-condensation of ketones is generally not favored in basic conditions, the self-condensed products do not form in the reaction between ketones and benzaldehyde. The general reaction of Claisen–Schmidt...
Biosynthesis of Polysaccharides
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Aldol Condensation with β-Diesters: Knoevenagel Condensation
β-Dicarbonyl Compounds via Crossed Claisen Condensations
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation


