title: Mechanistic studies on the cascade conversion of 1,3-dihydroxyacetone and formaldehyde into α-hydroxy-γ-butyrolactone.
abstract: The chemical synthesis of commercially and industrially important products from biomass-derived sugars is absolutely vital to establish biomass utilization as a sustainable alternative source of chemical starting materials. α-Hydroxy-γ-butyrolactone is a useful synthetic intermediate in pharmaceutical chemistry, and so novel biomass-related routes for its production may help to validate this eco-friendly methodology. Herein, we report the specific catalytic activity of homogeneous tin halides to convert the biomass-derived triose sugar 1,3-dihydroxyacetone and formaldehyde into α-hydroxy-γ-butyrolactone. A detailed screening of catalysts showed the suitability of tin catalysts for this reaction system, and isotope experiments using [D2]paraformaldehyde, substrate screening, and time profile measurements allowed us to propose a detailed reaction pathway. In addition, to elucidate the activated species in this cascade reaction, the effect of additional water and the influence of additional Brønsted acids on the reaction preferences for the formation of α-hydroxy-γ-butyrolactone, lactic acid, and vinyl glycolate were investigated. The active form of the Sn catalyst was investigated by (119)Sn NMR spectroscopy.
authors: Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259-G1-14 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan).
authors: Sho
authors: S
authors: Yamaguchi
authors: Takeaki
authors: T
authors: Matsuo
authors: Ken
authors: K
authors: Motokura
authors: Yasuharu
authors: Y
authors: Sakamoto
authors: Akimitsu
authors: A
authors: Miyaji
authors: Toshihide
authors: T
authors: Baba
mesh_terms: D015107:4-Butyrolactone / Q000737:chemistry*; D004098:Dihydroxyacetone / Q000737:chemistry*; D005557:Formaldehyde / Q000737:chemistry*; D007700:Kinetics; D014867:Water / Q000737:chemistry
chemical_list: D014867:Water; D005557:Formaldehyde; D004098:Dihydroxyacetone; D015107:4-Butyrolactone
keywords: biomass; homogeneous catalysis; reaction mechanisms; reactive intermediates; tin