Yamaguchi Sho, Matsuo Takeaki, Motokura Ken, Miyaji Akimitsu, Baba Toshihide
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.
Chem Asian J. 2016 Jun 6;11(11):1731-7. doi: 10.1002/asia.201600307. Epub 2016 May 9.
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.
我们报道了由生物质衍生的丙糖（1,3 - 二羟基丙酮）与各种醛类进行级联合成五元内酯的方法。这一成果为从单一生物质衍生糖生成多种有价值的化合物提供了一种新的合成策略。在几种被考察的路易斯酸催化剂中，均相氯化锡催化剂在形成碳 - 碳键方面表现出最佳性能。研究了使用醛类化合物合成五元内酯的范围和局限性。该级联反应具有高产物选择性和非对映选择性，并且基于异构化实验和密度泛函理论（DFT）计算对导致非对映选择性的机理进行了讨论。目前的结果有望为生物质衍生糖的高效利用提供新的方法。
