1-methyl-D-glucal | 187088-18-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1-methyl-D-glucal
• 英文别名: (2R,3S,4R)-2-(hydroxymethyl)-6-methyl-3,4-dihydro-2H-pyran-3,4-diol
• CAS: 187088-18-2
• 化学式: C₇H₁₂O₄
• 分子量: 160.17
• InChiKey: QGHULZMFRXAXFB-QYNIQEEDSA-N

物化性质

• 沸点：
  325.4±42.0 °C(Predicted)
• 密度：
  1.320±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  69.9
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-methyl-D-glucal 在 吡啶 、 4-二甲氨基吡啶 、 四丁基氟化铵 、 sodium cyanoborohydride 、 溶剂黄146 、 三乙胺 、 zinc(II) iodide 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 环己烷 、 乙酸乙酯 、 丙酮 为溶剂， 生成 N-((2R,3R,4R,5S,6R)-4,5-Dihydroxy-6-hydroxymethyl-2-methyl-tetrahydro-pyran-3-yl)-acetamide
  参考文献：
  名称：

  2-氨基C-葡糖苷和2-氨基C-葡糖苷spiroketals的合成

  摘要：

  偶氮二羧酸双（2,2,2-三氯乙基）酯在1-烷基葡糖上加成以提供[4 + 2]环加合物，所述环加合物又可以转化为2-氨基C-葡糖苷。该方法也适用于2-氨基C-葡糖苷螺缩酮的合成。

  DOI：

  10.1016/s0040-4039(00)93417-8
• 作为产物：
  描述：

  3-chloro-tri-O-benzyl-D-glucal 在 乙醇 、 仲丁基锂 、 sodium 作用下， 以 四氢呋喃 、 环己烷 、 氨 为溶剂， 生成 1-methyl-D-glucal
  参考文献：
  名称：

  The lithiation of 2-chloroglucal derivatives

  摘要：

  Lithiation of 2-chloroglucal derivatives provides ready access to the corresponding 1-lithioglucals which undergo a variety of serve useful intermediates for further elaboration of the carbohydrate nucleus. Removal of the 2-chloro substituent may be affected using a Birch-type reduction. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.09.087

文献信息

• Remarkable Oxidation Stability of Glycals: Excellent Substrates for Cerium(IV)-Mediated Radical Reactions
  作者：Torsten Linker、Dirk Schanzenbach、Elangovan Elamparuthi、Thomas Sommermann、Werner Fudickar、Viktor Gyóllai、László Somsák、Wolfgang Demuth、Michael Schmittel

  DOI：10.1021/ja8052706

  日期：2008.11.26

  rationale, which might be important for the redox behavior of other allylic systems. Finally, donors and acceptors in the 1-position exert the strongest influence on the oxidation stability, shifting the potentials by almost 1 V and resulting in different follow-up reactions of the cerium(IV)-mediated additions of malonates. It is the remarkable oxidation stability of glycals that makes them valuable

  通过它们在溶液中的氧化还原数据、计算的 HOMO 能量以及添加在硝酸铈 (IV) 铵存在下产生的亲电子自由基的行为，糖醛在氧化条件下的显着稳定性变得明显。获得了高达 2.03 V 与二茂铁的氧化电位，这对于环状烯醇醚来说非常高，但与自由基反应的反应时间密切相关。保护基团对氧化稳定性和糖类的 HOMO 能有很大影响，因为 E(ox) 从 O-甲硅烷基经过 O-苄基转移到 O-乙酰基超过 500 mV。有趣的是，这种效应必须通过 sigma 键传递，甚至高达苯甲酸酯基团的对位，正如碳水化合物中远程取代基的广泛变化所证实的那样。提出了相邻 CO 键的 sigma*-轨道与双键的 HOMO 的有利相互作用作为机械原理，这对于其他烯丙基系统的氧化还原行为可能很重要。最后，1 位的供体和受体对氧化稳定性的影响最大，将电位移动了近 1 V，并导致铈 (IV) 介导的丙二酸酯添加的不同后续反应。糖醛显着的
• Substituted glycals as probes of glycosidase mechanisms
  作者：Ellen C.K. Lai、Sandra A. Morris、Ian P. Street、Stephen G. Withers

  DOI：10.1016/s0968-0896(96)00175-7

  日期：1996.11

  D-Glucal and a series of substituted derivatives have been tested as substrates, inhibitors and inactivators of the Agrobacterium faecalis beta-glucosidase in order to probe structure/function relationships in this enzyme. D-Glucal is shown to be a substrate (k(cat)=2.3 min(-1), K-m=0.85 mM) undergoing hydration with stereospecific protonation from the alpha-face to yield 2-deoxy-beta-D-glucose. 1-Methyl-D-glucal surprisingly serves as only a poor substrate (k(cat)=0.056 min(-1), K-m=57 mM), also undergoing protonation from the alpha-face. 2-Fluoro-D-glucal, however, is completely inert, as a result of inductive destabilisation of the oxocarbenium ion-like transition state for protonation, and functions only as a relatively weak (K-i = 24 mM) inhibitor. Similar behaviour was seen with almond beta-glucosidase and yeast alpha-glucosidase and for the interaction of 2-fluoro-D-galactal with Escherichia coli beta-galactosidase. A series of of alpha,beta-unsaturated glucal derivatives was also synthesised and tested as potential substrates, inhibitors or inactivators of A. faecalis beta-glucosidase. Of these only 1-nitro-D-glucal functioned as a time dependent, irreversible inactivator (k(i)=0.011 min(-1), K-i=5.5 mM), presumably acting as a Michael acceptor. Electrospray mass spectrometric analysis revealed mutliple labeling of the enzyme by this inactivator, lessening its usefulness as an affinity label. Less reactive Michael acceptor glycals which might have been more specific (1-cyano-, 2-cyano-, 1-carboxylic acid, 1-carboxylic acid methyl ester) unfortunately did not function as inactivators or substrates, only as relatively weak reversible inhibitors (K-i=3-96 mM). Copyright (C) 1996 Elsevier Science Ltd