3,4,5,7-tetra-O-acetyl-2,6-anhydro-1-deoxy-D- | 74310-44-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3,4,5,7-tetra-O-acetyl-2,6-anhydro-1-deoxy-D-
• 英文别名: 3,4,5,7-tetra-O-acetyl-2,6-anhydro-1-deoxy-D-gluco-hept-1-enitol；[(2R,3R,4S,5R)-3,4,5-triacetyloxy-6-methylideneoxan-2-yl]methyl acetate
• CAS: 74310-44-4
• 化学式: C₁₅H₂₀O₉
• 分子量: 344.318
• InChiKey: WOTRYDYQXHDHQN-LXTVHRRPSA-N

物化性质

• 沸点：
  389.8±31.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3,4,5,7-tetra-O-acetyl-2,6-anhydro-1-deoxy-D- 在 sodium methylate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 (5R,7R,8S,9S,10R)-7-(hydroxymethyl)-3-(phenyl)-1,6-dioxa-2-azaspiro[4,5]dec-2-ene-8,9,10-triol
  参考文献：
  名称：

  1,3-Dipolar cycloaddition reactions on carbohydrate-based templates: synthesis of spiro-isoxazolines and 1,2,4-oxadiazoles as glycogen phosphorylase inhibitors

  摘要：

  1, 3-Dipolar cycloaddition of aryl nitrile oxides to benzyl/acetyl-protected exo-glucals and to a benzoylated glucosyl cyanide led in high yield to spiro-isoxazolines and to 3-aryl-5-glucosyl-1,2,4-oxadiazoles, respectively. The choice of the protective groups was important to the outcome of the cycloaddition and for the deprotection of the adducts. Cleavage of the ester protecting groups (acetyl, benzoyl) provided water-soluble spiro-isoxazolines and 3-aryl-5-glucosyl-1,2,4-oxadiazoles, evaluated as glycogen phosphorylase inhibitors. Preliminary tests showed IC50 values in the mu M range. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.06.058
• 作为产物：
  描述：

  葡萄糖酸内酯 在 咪唑 、 二氯二茂钛 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 142.0h， 生成 3,4,5,7-tetra-O-acetyl-2,6-anhydro-1-deoxy-D-
  参考文献：
  名称：

  外聚糖与芳基碘的立体选择性钯催化芳基化

  摘要：

  已经开发了一种用于外聚糖芳基化的新方法。在钯催化剂的存在下，一系列外聚糖与芳基碘化物发生反应。转化以立体选择性方式进行以提供Z-异构体。开发的转化表现出优异的官能团耐受性。

  DOI：

  10.1021/acs.joc.1c02533

文献信息

• An efficient synthesis of new 1′-C-methyl-α-O-disaccharides using 1-methylenesugars as the glycosyl donors
  作者：Xiaoliu Li、Hiro Ohtake、Hideyo Takahashi、Shiro Ikegami

  DOI：10.1016/s0040-4020(01)00319-2

  日期：2001.5

  A series of new 1′-C-methyl-α-disaccharides were firstly synthesized by the directly Lewis acid-catalyzed O-glycosidation of 1-methylenesugars used as glycosyl donors. The O-glycosidation afforded stereospecifically the corresponding 1′-methyl-α-O-glycosides whose configurations were tentatively assigned by the NMR spectra, COSY and the C–H coupling constant 3JH−2′,Me−1′. The O-glycosidation of the

  首先通过直接路易斯酸催化用作糖基供体的1-亚甲基糖的O-糖基化反应，合成了一系列新的1' - C-甲基-α-二糖。所述Ô -glycOSidation得到立体有择相应的1'-甲基α- ö -glycOSides其构型暂时由NMR谱，COSY和C-H分配耦合常数3 Ĵ H-2'中，Me-1' 。乙酰基保护的1-亚甲基糖的O-糖基化表明C-2- O处的乙酰基 由于形成叔氧碳鎓离子作为稳定的中间体，因此通过邻近基团的参与，该位置不能有效地控制产物的立体化学。
• C-Glycosylmethylene carbenes: synthesis of anhydro-aldose tosylhydrazones as precursors; generation and a new synthetic route to exo-glycals
  作者：Marietta Tóth、Katalin E. Kövér、Attila Bényei、László Somsák

  DOI：10.1039/b307378e

  日期：——

  Acylated anhydro-aldononitriles (glycosyl cyanides) were transformed into anhydro-aldose tosylhydrazones by Raney-nickel reduction in the presence of tosylhydrazine in a one-pot reaction. The configuration of the C=N double bond in these hydrazones was E as proven by 15N-1H coupling constants as well as X-ray crystallography. Thermolysis in refluxing 1,4-dioxane of the sodium salts of the tosylhydrazones

  在甲苯磺酰肼的一锅反应中，通过阮内镍还原将酰基化的脱水醛基腈（糖基氰化物）转化为脱水醛糖甲苯磺酰hydr。如15N-1H偶合常数和X射线晶体学所证明，在这些N中C ＝ N双键的构型为E。由氢化钠（通常为10当量）获得的甲苯磺酰hydr的钠盐在回流的1，4-二恶烷中的热分解导致形成脱水-1-脱氧醛-1-烯醇（外糖）。当使用较少的碱导致起始化合物的不完全去质子化时，也可以分离出“二聚” N-糖基甲基脱水醛糖糖基hydr。该两步过程构成了从容易获得的糖基氰化物到酰化外糖的新颖，相当短的合成途径。
• Efficiency of the Free-Radical Hydrophosphonylation of Alkenes: The Photoinduced Reaction of Dimethyl<i>H</i>-Phosphonate with Enopyranoses as an Exemplary Case
  作者：Alessandro Dondoni、Samuele Staderini、Alberto Marra

  DOI：10.1002/ejoc.201300780

  日期：2013.8

  Free-radical hydrophosphonylation of alkenes by H-phosphonates has been reported by other groups to occur under harsh conditions. On the other hand, we demonstrate in this paper that the hydrophosphonylation of alkene functionalized carbohydrates (enopyranoses) by dimethyl H-phosphonate can be carried out with high efficiency under neutral conditions at room temperature and with short reaction times

  H-膦酸酯对烯烃的自由基氢膦酰化已被其他研究小组报道在恶劣条件下发生。另一方面，我们在本文中证明，在室温下中性条件下，使用 UV/Vis 光照射可以在较短的反应时间内高效地进行 H-膦酸二甲酯对烯烃官能化碳水化合物（烯吡喃糖）的氢膦酰化。存在合适的光引发剂。事实上，一系列结构不同的烯丙基 C-糖苷和外切糖苷被转化为相应的糖基烷基膦酸酯，以优异的产率 (88-98%) 分离，除了一个例子 (45%)。提出了一种类似于自由基光诱导烯烃氢硫醇化的机制。
• [2+2] Cycloadditions of Methylene <i>exo</i> ‐Glycals: Synthesis of Glycopyranosylidene‐Spiro‐Azetidine‐2‐ones (β‐Lactams) and Cyclobutanones
  作者：János József、László Somsák、Marietta Tóth、László Juhász

  DOI：10.1002/ejoc.202201488

  日期：2023.3.21

  New anomeric spiro-β-lactam and spiro-cyclobutanone derivatives were synthesized by [2+2] cycloadditions of methylene exo-glycals with chlorosulfonyl isocyanate and dichloroketene. The reactions were studied in detail, investigating the effect of carbohydrate moiety, protecting groups as well as reaction temperature on the yields. The transformation of spiro-cyclobutanone into spiro-γ-lactone was demonstrated

  通过亚甲基外切-glycals 与氯磺酰异氰酸酯和二氯乙烯酮的 [2+2] 环加成反应合成了新的异头螺-β-内酰胺和螺-环丁酮衍生物。详细研究了反应，研究了碳水化合物部分、保护基团以及反应温度对产率的影响。证明了螺-环丁酮向螺-γ-内酯的转化。
• Glucose-derived spiro-isoxazolines are anti-hyperglycemic agents against type 2 diabetes through glycogen phosphorylase inhibition
  作者：David Goyard、Bálint Kónya、Aikaterini S. Chajistamatiou、Evangelia D. Chrysina、Jérémy Leroy、Sophie Balzarin、Michel Tournier、Didier Tousch、Pierre Petit、Cédric Duret、Patrick Maurel、László Somsák、Tibor Docsa、Pál Gergely、Jean-Pierre Praly、Jacqueline Azay-Milhau、Sébastien Vidal

  DOI：10.1016/j.ejmech.2015.12.004

  日期：2016.1

  Glycogen phosphorylase (GP) is a target for the treatment of hyperglycaemia in the context of type 2 diabetes. This enzyme is responsible for the depolymerization of glycogen into glucose thereby affecting the levels of glucose in the blood stream. Twelve new D-glucopyranosylidene-spiro-isoxazolines have been prepared from O-peracylated exo-D-glucals by regio- and stereoselective 1,3-dipolar cycloaddition of nitrile oxides generated in situ by treatment of the corresponding oximes with bleach. This mild and direct procedure appeared to be applicable to a broad range of substrates. The corresponding 0-unprotected spiro-isoxazolines were evaluated as glycogen phosphorylase (GP) inhibitors and exhibited IC50 values ranging from 1 to 800 mu M. Selected inhibitors were further evaluated in vitro using rat and human hepatocytes and exhibited significant inhibitory properties in the primary cell culture. Interestingly, when tested with human hepatocytes, the tetra-O-acetylated spiro-isoxazoline bearing a 2-naphthyl residue showed a much lower IC50 value (2.5 mu M), compared to that of the 0-unprotected analog (19.95 mu M). The most promising compounds were investigated in Zucker fa/fa rat model in acute and sub-chronic assays and decreased hepatic glucose production, which is known to be elevated in type 2 diabetes. This indicates that glucose-based spiro-isoxazolines can be considered as anti-hyperglycemic agents in the context of type 2 diabetes. (C) 2015 Elsevier Masson SAS. All rights reserved.