1,5-脱水-d-果糖 | 75414-43-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 中文名称: 1,5-脱水-d-果糖
• 英文名称: 1,5-D-anhydrofructose
• 英文别名: 1,5-anhydro-d-fructose；(4S,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)oxan-3-one
• CAS: 75414-43-6
• 化学式: C₆H₁₀O₅
• 分子量: 162.142
• InChiKey: OCLOLUFOLJIQDC-HSUXUTPPSA-N

物化性质

• 熔点：
  44-47°C
• 沸点：
  405.0±45.0 °C(Predicted)
• 密度：
  1.521±0.06 g/cm3(Predicted)
• 溶解度：
  少量溶于甲醇和水

计算性质

• 辛醇/水分配系数(LogP)：
  -1.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  87
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,5-脱水-d-果糖 在 palladium on activated charcoal 吡啶 、 4-二甲氨基吡啶 、 氢气 、 sodium methylate 、 三溴化硼 作用下， 以 甲醇 、 乙醇 、 氯仿 为溶剂， -20.0~20.0 ℃ 、3.0 MPa 条件下， 反应 147.0h， 生成 1-脱氧甘露伊霉素
  参考文献：
  名称：

  1,5-Anhydro-d-fructose as Chiral Building Block: A Novel Approach to 1-Deoxymannojirimycin

  摘要：

  报告了一种从1,5-无水-d-果糖合成1-脱氧甘露糖苷霉素的新型六步法，总体产率为35%。关键步骤是亲核性哌啶环的形成以及随后路易斯酸诱导的吡喃醚裂解。

  DOI：

  10.1055/s-2006-926343
• 作为产物：
  描述：

  3,4,6-tri-O-benzyl-1,5-anhydro-D-fructose 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 48.0h， 以91%的产率得到1,5-脱水-d-果糖
  参考文献：
  名称：

  Expedient conversion of d-glucose into 1,5-anhydro-d-fructose and into single stereogenic-center dihydropyranones, suitable six-carbon scaffolds for concise syntheses of the soft-coral constituents (−)-bissetone and (−)-palythazine

  摘要：

  High-yielding protocols are described to convert D-glucose-via hydroxylaminolysis of its hydroxyglucal esters, followed by deoximination and beta-elimination of acid-into dihydropyranone building blocks with a single stereogenic center. Their versatility as enantiopure six-carbon scaffolds is highlighted by excellent regio- and stereocontrol in a variety of addition reactions and by their straightforward use as building blocks for the concise syntheses of the soft-coral constituents bissetone and palythazine in enantiopure form, thereby proving their absolute configuration. Moreover, several procedures are detailed to convert hydroxyglucal esters into 1,5-anhydro-D-fructose, their parent sugar, the direct low-temperature de-O-acylation being the most suitable for preparative purposes, as long as its access via enzymatic degradation of starch is not implemented on an appreciable scale. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.01.019

文献信息

• Purification, Characterization, and Molecular Cloning of a Pyranose Oxidase from the Fruit Body of the Basidiomycete,<i>Tricholoma matsutake</i>
  作者：Yoshimitsu TAKAKURA、Shigeru KUWATA

  DOI：10.1271/bbb.67.2598

  日期：2003.1

  A new H2O2-generating pyranose oxidase was purified as a strong antifungal protein from an arbuscular mycorrhizal fungus, Tricholoma matsutake. The protein showed a molecular mass of 250 kDa in gel filtration, and probably consisted of four identical 62 kDa subunits. The protein contained flavin moiety and it oxidized D-glucose at position C-2. H2O2 and D-glucosone produced by the pyranose oxidase reaction showed antifungal activity, suggesting these compounds were the molecular basis of the antifungal property. The Vmax, Km, and kcat for D-glucose were calculated to be 26.6 U/mg protein, 1.28 mM, and 111/s, respectively. The enzyme was optimally active at pH 7.5 to 8.0 and at 50°C. The preferred substrate was D-glucose, but 1,5-anhydro-D-glucitol, L-sorbose, and D-xylose were also oxidized at a moderate level. The cDNA encodes a protein consisting of 564 amino acids, showing 35.1% identity to Coriolus versicolor pyranose oxidase. The recombinant protein was used for raising the antibody.

  从一种内生菌根真菌松口蘑中纯化得到一种新的H2O2生成吡喃糖氧化酶，该酶具有强烈的抗真菌蛋白活性。该蛋白在凝胶过滤中表现出250 kDa的分子质量，可能由四个相同的62 kDa亚基组成。该蛋白含有黄素部分，并在C-2位置氧化D-葡萄糖。由吡喃糖氧化酶反应产生的H2O2和D-葡糖酮具有抗真菌活性，表明这些化合物是其抗真菌特性的分子基础。D-葡萄糖的Vmax、Km和kcat分别为26.6 U/mg蛋白、1.28 mM和111/s。该酶在pH 7.5至8.0和50°C下活性最佳。其首选底物是D-葡萄糖，但1,5-脱水-D-山梨醇、L-山梨糖和D-木糖也能在中等程度上被氧化。该cDNA编码一个由564个氨基酸组成的蛋白质，与杂色革盖菌的吡喃糖氧化酶有35.1%的同源性。使用重组蛋白制备抗体。
• [EN] METHOD FOR THE PRODUCTION OF GLYCOLS FROM AN ANHYDROSUGAR FEED<br/>[FR] PROCÉDÉ DE PRODUCTION DE GLYCOLS À PARTIR D'UNE CHARGE D'ANHYDROSUCRE
  申请人：SHELL OIL CO

  公开号：WO2018039109A1

  公开（公告）日：2018-03-01

  Implementations of the disclosed subject matter provide a method for producing glycols from an anhydrosugar feed. The method may include contacting, in a reactor under hydrogenolysis conditions, the anhydrosugar feed with a bi-functional catalyst system. The bi-functional catalyst system may include a retro-Aldol catalyst and a hydrogenation catalyst. A product stream may be obtained from the first reactor including ethylene glycol and propylene glycol.

  所披露的主题实施提供了一种从无水糖原料生产乙二醇的方法。该方法可能包括在氢解条件下，在反应器中将无水糖原料与双功能催化剂系统接触。双功能催化剂系统可能包括逆Aldol催化剂和加氢催化剂。从第一反应器中可以获得包括乙二醇和丙二醇的产品流。
• Fungal enzymic activity degrading 1,4-α-d-glucans to. 1,5-d-anhydrofructose
  作者：Marie-Antoinette Baute、Robert Baute、Gérard Deffieux

  DOI：10.1016/0031-9422(88)80738-6

  日期：1988.1

  Abstract 1,5- d -Anhydrofructose, the precursor of the antibiotic pyrone microthecin in morels and other fungi, is produced in Morchella vulgaris by a novel enzymic activity, presumably a lyasic one, which acts specifically on open-chain 1,4-α- d -glucans; it can be prepared enzymatically in vitro from starch in 40 to 50% yield.

  摘要 1,5-d-脱水果糖是羊肚菌和其他真菌中抗生素吡喃微囊素的前体，在羊肚菌中通过一种新的酶活性产生，可能是裂解酶，它专门作用于开链 1,4-α - d -葡聚糖；它可以在体外由淀粉酶促制备，产率为 40% 至 50%。
• Formation of 4-deoxy-glycero-hexo-2,3-diulo-furanose from microthecin
  作者：Anders Broberg、Lennart Kenne、Marianne Pedersén

  DOI：10.1016/s0008-6215(97)10045-3

  日期：1998.1

  formed from microthecin [2-hydroxy-2-(hydroxymethyl)-2H-pyran-3(6H)-one] in neutral water solutions by a Michael addition. The compound was determined by NMR spectroscopy, MS and polarimetry to be a racemic mixture of d -and l -forms and existing mainly as two furanosidic C-2 epimers in equilibrium with microthecin. GC–MS analysis showed that 4-deoxy-glycero-hexo-2,3-diulose and microthecin were present

  摘要在中性水溶液中，通过迈克尔加成反应，由微素[2-羟基-2-（羟甲基）-2H-吡喃-3（6H）-一]形成了4-脱氧-己基-2,3-二醛。通过NMR光谱法，MS和旋光法测定该化合物为d-和l-型的外消旋混合物，并且主要以与呋喃霉素平衡的两个呋喃硅C-2差向异构体存在。GC-MS分析表明，红藻Gracilariopsis lemaneiformis的提取物中存在4-deoxy-glycero-hexo-2,3-diulose和microthecin。
• A convenient access to 1,5-anhydroketoses
  作者：F.W. Lichtenthaler、E.S.H. El Ashry、V.H. Göckel

  DOI：10.1016/s0040-4039(00)92737-0

  日期：——

  A convenient, versatile entry into the 1,5-anhyroketose series is described and their conversion into enolones, enolone oximes and γ-pyrones.

  描述了一种方便，通用的进入1,5-脱水酮糖系列的方法，并将其转换为烯醇酮，烯醇酮肟和γ-吡喃酮。