钼酸催化简便合成D-葡萄庚酮糖  

Concise Synthesis of D-Glucoheptulose under Molybdic Acid-Catalysis

作　　者：程杰[1] 方志杰[1] 焦岩[1] 姜宇华[1] 郑保辉[1] 

机构地区：[1]南京理工大学化工学院南京210094

出　　处：《应用化学》2009年第7期749-752,共4页Chinese Journal of Applied Chemistry

摘　　要：在三氧化钼水溶液体系中催化碳链重排合成了D-葡萄庚酮糖。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%)。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。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。This article reports a method for the synthesis of D-glucoheptulose by catalyzing carbon-skeleton rearrangement in 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 a yield of 90%. Secondly, hydroxymethylation on the C-2 of 2, 3：5,6-Di-O-isopropylidene-D-mannose occurred with formaldehyde aqueous solution under base condition, with a yield of 40%. Thirdly, 2-C-hydroxymethyl-D-mannose was prepared through the deprotection of isopropyaltion reaction under acid condition with a yield of 92%. And finally, D-glucoheptulose was synthesized by molybdic acid-catalyzed carbon-skeleton rearrangement with a yield of 56% （ total yield 18% ）. In addition, the acetylated products of 2-C-hydroxymethyl-D-mannose and D-glucoheptulose were characterized by 1H NMR. The advantages of the method includ readily acquiring of materials, simplifying of the reaction procedures, and avoiding the application of expensive metal reagents with a good foreground of industrial application.

关 键 词：钼酸 D-葡萄庚酮糖 碳链重排 合成 

分 类 号：O626.2[理学—有机化学]