钼酸催化简便合成D－葡萄庚酮糖

本文首次报道了在三氧化钼水溶液体系下催化碳链重排合成D-葡萄庚酮糖的简便方法。首先以D-甘露糖为原料在碘催化下进行异丙叉保护，产率90％；接着在碱催化下与甲醛水溶液亲核加成反应，在C-2上引入羟甲基侧链，产率40％；然后在酸性条件下异丙叉脱保护，产率92％；最后在三氧化钼水溶液催化下碳链重排合成葡萄庚酮糖，产率56％（总产率18％）。另外对2-C-羟甲基-D-甘露糖和葡萄庚酮糖的乙酰化产物进行了核磁氢谱表征。该方法原料易得，缩短了反应步骤，避免了昂贵金属试剂的使用，有较好的应用前景。

Concise Synthesis of D-Glucoheptulose by Molybdic Acid-Catalyzed

This article reports a new concise method of synthesis of D-glucoheptulose by catalyzed carbon-skeleton rearrangement under the system of MoO3 aqueous solution. Firstly, 2,3:5,6 -Di-O-isopropylidene-D-mannose was prepared from D-mannose as starting material under the catalyst of iodine, with yield 90%. Secondly, hydroxymethylation on C-2 of 2,3:5,6-Di-O-isopropylidene -D-mannose occurred with formaldehyde aqueous solution under base condition, with yield 40%. Thirdly, 2-C-hydroxymethyl-D-mannose was prepared through deprotection of isopropyaltion reaction under acid condition with the yield of 92%. And finally, D-glucoheptulose was synthesized by molybdic acid-catalyzed carbon-skeleton rearrangement with the yield of 56%(total yield 18%). In addition, the acetylated products of 2-C-hydroxymethyl-D-mannose and D-glucoheptulose were characterized by 1HNMR. The advantages of the method included easily acquiring of materials, reducing the reaction procedures, avoiding the application of expensive metal reagents and well foreground of industrial application.