(2R,3R,4S,5S,6R)-2-[[(2R,3S,4R)-4-羟基-2-(羟基甲基)-3,4-二氢-2H-吡喃-3-基]氧基]-6-(羟基甲基)四氢吡喃-3,4,5-三醇 | 32447-71-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (2R,3R,4S,5S,6R)-2-[[(2R,3S,4R)-4-羟基-2-(羟基甲基)-3,4-二氢-2H-吡喃-3-基]氧基]-6-(羟基甲基)四氢吡喃-3,4,5-三醇
• 英文名称: maltal
• 英文别名: (2R,3R,4S,5S,6R)-2-[[(2R,3S,4R)-4-hydroxy-2-(hydroxymethyl)-3,4-dihydro-2H-pyran-3-yl]oxy]-6-(hydroxymethyl)oxane-3,4,5-triol
• CAS: 32447-71-5
• 化学式: C₁₂H₂₀O₉
• 分子量: 308.285
• InChiKey: HNXRLRRQDUXQEE-YKDNNCFHSA-N

物化性质

• LogP：
  -3.877 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  -3.1
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  149
• 氢给体数：
  6
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (2R,3R,4S,5S,6R)-2-[[(2R,3S,4R)-4-羟基-2-(羟基甲基)-3,4-二氢-2H-吡喃-3-基]氧基]-6-(羟基甲基)四氢吡喃-3,4,5-三醇 在 咪唑 、 混旋樟脑磺酸 、 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.17h， 生成 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranosyl-(1→4)-1,5-anhydro-3-O-benzyl-2-deoxy-D-arabino-hex-1-enitol
  参考文献：
  名称：

  From 1,4-Disaccharide to 1,3-Glycosyl Carbasugar: Synthesis of a Bespoke Inhibitor of Family GH99 Endo-α-mannosidase

  摘要：

  Understanding the enzyme reaction mechanism can lead to the design of enzyme inhibitors. A Claisen rearrangement was used to allow conversion of an alpha-1,4-disaccharide into an alpha-1,3-linked glycosyl carbasugar to target the endo-alpha-mannosidase from the GH99 glycosidase family, which, unusually, is believed to act through a 1,2-anhydrosugar "epoxide" intermediate. Using NMR and X-ray crystallography, it is shown that glucosyl carbasugar alpha-aziridines can act as reasonably potent endo-alpha-mannosidase inhibitors, likely by virtue of their shape mimicry and the interactions of the aziridine nitrogen with the conserved catalytic acid/base of the enzyme active site.

  DOI：

  10.1021/acs.orglett.8b03260
• 作为产物：
  描述：

  α-hepta-O-acetylmaltosyl bromide 在 甲醇 、 氨 、 溶剂黄146 、 锌 作用下， 生成 (2R,3R,4S,5S,6R)-2-[[(2R,3S,4R)-4-羟基-2-(羟基甲基)-3,4-二氢-2H-吡喃-3-基]氧基]-6-(羟基甲基)四氢吡喃-3,4,5-三醇
  参考文献：
  名称：

  Haworth et al., Journal of the Chemical Society, 1934, p. 302

  摘要：

  DOI：

文献信息

• N-Heterocyclic Carbene Catalyzed <i>C</i>-Glycosylation: A Concise Approach from Stetter Reaction
  作者：Seenuvasan Vedachalam、Shi Min Tan、Hui Ping Teo、Shuting Cai、Xue-Wei Liu

  DOI：10.1021/ol202959y

  日期：2012.1.6

  Described herein is the first example of an organocatalytic approach for acylanion addition to the anomeric carbon of 2-nitroglucal using an N-heterocyclic carbene catalyst. Control over the reaction conditions gives β-selective and nitro-eliminated C-glycosides, providing opportunities to produce new classes of C-glycoside.

  在此描述的是使用N-杂环卡宾催化剂将酰基丙氨酸加成到2-硝基葡萄糖醛的异头碳中的有机催化方法的第一个例子。控制反应条件使β选择性和硝基消除Ç -glycosides，提供机会，以产生新的类Ç糖苷。
• Base-catalyzed degradation of permethylated 3-O-glycosyl-glycopyranosid-2-uloses
  作者：Gerald O. Aspinall、Peter Capek、Roshan C. Carpenter、Janusz Szafranek

  DOI：10.1016/s0008-6215(00)90533-0

  日期：1991.8

  modification of the Svensson degradation, otherwise permethylated glycopyranosid-2-uloses bearing 4-O-glycosyl substituents are formed by the Swern oxidation. Base-catalyzed elimination on treatment with triethylamine then gives 4-deoxy-3-O-methylglyc-3-enopyranosid-2-ulose-terminat ed oligosaccharides with liberation of glycosyl substituents as reducing sugars but without further degradation. Mild acid hydrolysis

  在Svensson降解的改进中，通过Swern氧化形成否则带有4-O-糖基取代基的全甲基化的吡喃葡萄糖苷-2-ulose。然后用三乙胺进行碱催化消除，得到4-脱氧-3-O-甲基糖-3-烯吡喃糖基-2-葡萄糖端基化的寡糖，其中糖基取代基释放为还原糖，但没有进一步降解。轻度的酸水解导致不饱和糖残基的去除，从而整体解聚发生，而最初氧化的糖残基仅净损失。
• Synthesis of 2-deoxy cyclic and linear oligosaccharides by oligomerization of monomers
  作者：Somak Paul、Srinivasarao Raghothama、Narayanaswamy Jayaraman

  DOI：10.1016/j.carres.2008.10.026

  日期：2009.1

  Cyclic and linear oligosaccharides constituted with 2-deoxy sugar units are synthesized by an oligomerization reaction involving activated thioglycoside monomers, consisting of a 2-deoxy sugar unit. The oligomerization promoter plays an important role in the formation of either the cyclic- or the linear oligosaccharides. Encapsulation abilities of a 2-deoxy cyclic hexamer with p-nitrophenot, by a H-1 NMR method, showed complexation of the guest molecule with the host molecule. (C) 2008 Elsevier Ltd. All rights reserved.
• Haworth et al., Journal of the Chemical Society, 1934, p. 302
  作者：Haworth et al.

  DOI：——

  日期：——
• From 1,4-Disaccharide to 1,3-Glycosyl Carbasugar: Synthesis of a Bespoke Inhibitor of Family GH99 Endo-α-mannosidase
  作者：Dan Lu、Sha Zhu、Lukasz F. Sobala、Ganeko Bernardo-Seisdedos、Oscar Millet、Yongmin Zhang、Jesus Jiménez-Barbero、Gideon J. Davies、Matthieu Sollogoub

  DOI：10.1021/acs.orglett.8b03260

  日期：2018.12.7

  Understanding the enzyme reaction mechanism can lead to the design of enzyme inhibitors. A Claisen rearrangement was used to allow conversion of an alpha-1,4-disaccharide into an alpha-1,3-linked glycosyl carbasugar to target the endo-alpha-mannosidase from the GH99 glycosidase family, which, unusually, is believed to act through a 1,2-anhydrosugar "epoxide" intermediate. Using NMR and X-ray crystallography, it is shown that glucosyl carbasugar alpha-aziridines can act as reasonably potent endo-alpha-mannosidase inhibitors, likely by virtue of their shape mimicry and the interactions of the aziridine nitrogen with the conserved catalytic acid/base of the enzyme active site.