We report on a new route to produce hexane-1,2,5,6-tetrol (tetrol) from cellulose-derived levoglucosanol (lgol). We investigate the reaction intermediates formed over metal and acid catalysts, and propose a reaction network for this process. Lgol is converted to tetrol in up to 90% yield over a bifunctional Pt/SiO₂–Al₂O₃ catalyst at 150 °C. High tetrol yields are maintained at lgol concentrations of up to 21 wt% in water. threo- and erythro-lgol first undergo hydrolysis to 3,4-dideoxymannose (DDM) and 3,4-dideoxyglucose (DDG), respectively. This reaction can be carried out selectively over an Amberlyst 70 acid catalyst at a temperature of 100 °C. At a higher temperature of 150 °C with no added catalyst, DDM and DDG undergo aldose–ketose isomerization to 3,4-dideoxyfructose (DDF). DDM is hydrogenated to cis-tetrol over a Pt/SiO₂ catalyst, while DDG is hydrogenated to trans-tetrol. Formation of DDF erases the stereocenter at the C₂ position of lgol, and hydrogenation of DDF produces a nearly 1 : 1 mixture of cis- and trans-tetrol. This catalytic approach to produce tetrol from biomass opens the door to sustainable chemicals derived from tetrol.

中文翻译：

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生物可再生左旋葡糖醇在水中催化生产1,2,5,6-四氢呋喃：金属和酸性部位对（立体）选择性的影响

我们报告了从纤维素衍生的左旋葡萄糖醇（lgol）生产己烷-1,2,5,6-tetrol（tetrol）的新途径。我们研究了在金属和酸催化剂上形成的反应中间体，并提出了该过程的反应网络。在150°C下，在双功能Pt / SiO ₂ -Al ₂ O ₃催化剂上，Lgol可以高达90％的产率转化为四氢萘酚。在水中高达21 wt％的lgol浓度下，保持高四苯酚产量。苏-和赤-lgol首先分别水解为3,4-二脱氧甘露糖（DDM）和3,4-二脱氧葡萄糖（DDG）。该反应可以在100℃的温度下在Amberlyst 70酸催化剂上选择性地进行。在不添加催化剂的情况下，在150°C的较高温度下，DDM和DDG会经历醛糖-酮糖异构化为3,4-二脱氧果糖（DDF）。在Pt / SiO ₂催化剂上将DDM氢化为顺式-四醇，而将DDG氢化为反式-四醇。DDF的形成消除了lgol C ₂位置的立体中心，DDF的氢化产生顺式和反式的近1：1混合物-tetrol。这种由生物质生产四氢萘的催化方法为源自四氢萘的可持续化学品打开了大门。