title: Cascade Synthesis of Five-Membered Lactones using Biomass-Derived Sugars as Carbon Nucleophiles.
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.
authors.affiliation: Department 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.
authors.forename: Sho
authors.initials: S
authors.lastname: Yamaguchi
authors.affiliation: Department 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.
authors.forename: Takeaki
authors.initials: T
authors.lastname: Matsuo
authors.affiliation: Department 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.
authors.forename: Ken
authors.initials: K
authors.lastname: Motokura
authors.affiliation: Department 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.
authors.forename: Akimitsu
authors.initials: A
authors.lastname: Miyaji
authors.affiliation: Department 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.
authors.forename: Toshihide
authors.initials: T
authors.lastname: Baba
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D018533:Biomass; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D007783:Lactones / Q000138:chemical synthesis / Q000737:chemistry*; D058116:Lewis Acids / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D011789:Quantum Theory; D013237:Stereoisomerism; D000073893:Sugars / Q000737:chemistry*; D013816:Thermodynamics; D017971:Tin Compounds / Q000737:chemistry
chemical_list: D000447:Aldehydes; D007783:Lactones; D058116:Lewis Acids; D000073893:Sugars; D017971:Tin Compounds; C023599:stannous chloride; D002244:Carbon
keywords: 1,3-dihydroxyacetone; biomass conversion; cascade reactions; five-membered lactones; homogeneous catalysis