3,4,5,7-tetra-O-benzoyl-2,6-anhydro-1-deoxy-D-gluco-hept-1-enitol

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,4,5,7-tetra-O-benzoyl-2,6-anhydro-1-deoxy-D-gluco-hept-1-enitol
• 英文别名: [(2R,3R,4S,5R)-3,4,5-tribenzoyloxy-6-methylideneoxan-2-yl]methyl benzoate
• 化学式: C₃₅H₂₈O₉
• 分子量: 592.602
• InChiKey: OTGBRYDDXOPUBU-YXOGWZJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  44
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  吲哚-3-甲醛肟 、 3,4,5,7-tetra-O-benzoyl-2,6-anhydro-1-deoxy-D-gluco-hept-1-enitol 在 sodium hypochlorite 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 16.0h， 以202 mg的产率得到(5R,7R,8R,9S,10R)-8,9,10-tris(benzoyloxy)-7-(benzoyloxymethyl)-1,6-dioxa-3-(indol-3-yl)-2-azaspiro[4,5]dec-2-ene
  参考文献：
  名称：

  Glucose-derived spiro-isoxazolines are anti-hyperglycemic agents against type 2 diabetes through glycogen phosphorylase inhibition

  摘要：

  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.

  DOI：

  10.1016/j.ejmech.2015.12.004
• 作为产物：
  描述：

  (2R,3R,4R,5S,6S)-2-[(苯甲酰氧基)甲基]-6-氰基四氢-2H-吡喃-3,4,5-三基三苯甲酸酯 在 镍 吡啶 、 sodium hypophosphite 、 sodium hydride 作用下， 以 1,4-二氧六环 、 溶剂黄146 为溶剂， 反应 2.0h， 生成 3,4,5,7-tetra-O-benzoyl-2,6-anhydro-1-deoxy-D-gluco-hept-1-enitol
  参考文献：
  名称：

  C-糖基亚甲基卡宾：以脱水醛糖甲苯磺酰hydr为前体的合成；代和新的合成途径合成外糖。

  摘要：

  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。

  DOI：

  10.1039/b307378e

文献信息

• Coupling of <i>N</i>-tosylhydrazones with tetrazoles: synthesis of 2-β-<scp>d</scp>-glycopyranosylmethyl-5-substituted-2<i>H</i>-tetrazole type glycomimetics
  作者：Tímea Kaszás、Ivett Cservenyák、Éva Juhász-Tóth、Andrea E. Kulcsár、Paola Granatino、Ulf J. Nilsson、László Somsák、Marietta Tóth

  DOI：10.1039/d0ob02248a

  日期：——

  The first tosylhydrazone-tetrazole coupling provides a straightforward access to a new type of glycomimetics with exclusive regioselectivity.

  第一次甲磺酰肼-四唑偶联反应为一种具有独特区域选择性的新型糖类模拟物提供了一种直接途径。
• Systematic study on free radical hydrothiolation of unsaturated monosaccharide derivatives with exo- and endocyclic double bonds
  作者：László Lázár、Magdolna Csávás、Ádám Hadházi、Mihály Herczeg、Marietta Tóth、László Somsák、Terézia Barna、Pál Herczegh、Anikó Borbás

  DOI：10.1039/c3ob40547h

  日期：——

  reacted with various thiols by irradiation with UV light in the presence of a cleavable photoinitiator. The photoinduced radical-mediated hydrothiolation reactions showed highly varying overall conversions depending not only on the substitution pattern and electron-density of the double bond but also on the nature and substitution pattern of the thiol partner. Out of the applied thiols thiophenol, producing

  通过在可裂解的光引发剂的存在下用紫外线照射，使糖的外环和内环双键以及烯键的末端双键与各种硫醇反应。光诱导的自由基介导的氢硫醇化反应显示出很大变化的总转化率，这不仅取决于双键的取代方式和电子密度，还取决于硫醇配偶体的性质和取代方式。在所施加的硫醇中，产生高度稳定的噻吩基的硫酚对每种烯烃的反应性最低。在大多数情况下，氢硫醇化反应具有完全的区域选择性和立体选择性。将1,2：3,4-二-O-异亚丙基-6-硫代-α- D-吡喃半乳糖成功添加到2,3-不饱和N-乙酰神经氨酸衍生物提供（3→6）-S连接的假二糖，表明带有吸电子取代基的Neu5Ac-2-ene的内环双键在光诱导的硫醇-烯偶联反应中显示出足够的反应性。 。
• A new synthesis of C-β-<scp>d</scp>-glycopyranosylmethyl sulfides by metal-free coupling of anhydro-aldose tosylhydrazones with thiols
  作者：Tímea Kaszás、Marietta Tóth、László Somsák

  DOI：10.1039/c7nj03069j

  日期：——

  Herein, cross coupling reactions of O-peracylated 2,6-anhydro-aldose tosylhydrazones with aliphatic, (hetero)aromatic, and sugar-derived thiols were studied under thermal conditions in the presence of K3PO4. The reactions with aliphatic thiols provided the corresponding C-β-D-glycopyranosylmethyl sulfides in 20–50% yields, whereas the reactions with thiophenols gave the corresponding sulfides in 50–80%

  在此，在K 3 PO 4存在下，在热条件下研究了O-过酰化的2，6-脱水醛糖甲苯磺酰with与脂族，（杂）芳族和糖衍生的硫醇的交叉偶联反应。与脂族硫醇的反应以20–50％的收率提供了相应的C- β- D-甘露糖基甲基硫化物，而与硫酚的反应以50–80％的收率提供了相应的硫化物。另一方面，糖衍生的硫醇未能以可接受的选择性产生预期的化合物。转化为获得这些类型的拟糖化合物提供了新途径。该方法是对exo的硫醇添加的补充-二醇（也可从上述甲苯磺酰obtained获得）提供良好的脂族和糖衍生的C-糖基甲基硫化物的收率。因此，无论是在直接偶联反应中，还是在硫醇-烯加成外糖的情况下，脱水醛糖甲苯磺酰hydr都可以用作任何一种C-糖基甲基硫化物类型目标化合物的常用原料。
• Coupling of anhydro-aldose tosylhydrazones with hydroxy compounds and carboxylic acids: a new route for the synthesis of C-β-<scp>d</scp>-glycopyranosylmethyl ethers and esters
  作者：Tímea Kaszás、Marietta Tóth、Sándor Kun、László Somsák

  DOI：10.1039/c6ra27282g

  日期：——

  tosylhydrazones) with alcohols, phenols, and carboxylic acids were studied under thermic or photolytic conditions in the presence of K3PO4 or LiOtBu. The reactions failed with EtOH, BnOH, or tBuOH, however, (CF3)2CHOH, electron poor phenols and carboxylic acids gave the corresponding C-β-D-glycopyranosylmethyl ethers and esters, respectively, representing a new access to these glycomimetic compounds.

  在K 3 PO 4存在下，在热或光解条件下研究了O-过酰化的2，6-脱水醛糖甲苯磺酰yl（C-（β- D-甘露糖基）甲醛甲苯磺酰to）与醇，酚和羧酸的交叉偶联。或LiO t Bu。用EtOH，BnOH或t BuOH可使反应失败，但是，（CF 3）2 CHOH，电子贫乏的酚和羧酸分别产生相应的C- β- D-糖基核糖基甲基醚和酯，代表了使用这些糖模拟物的新途径化合物。
• Pd-catalyzed coupling reactions of anhydro-aldose tosylhydrazones with aryl bromides to produce substituted exo -glycals
  作者：Tímea Kaszás、Anton Ivanov、Marietta Tóth、Peter Ehlers、Peter Langer、László Somsák

  DOI：10.1016/j.carres.2018.02.010

  日期：2018.8

  Palladium-catalyzed cross-couplings of O-peracylated and O-permethylated 2,6-anhydro-aldose tosylhydrazones with aryl halides were studied under thermic conditions in the presence of LiOtBu and phosphine ligands. The reactions gave the corresponding aryl substituted exo-glycals as mixtures of diastereomers in 11-75% yields. The transformations represent a new access to these types of glycomimetic compounds

  在LiOtBu和膦配体的存在下，在热条件下研究了钯催化的O-过酰基化和O-过甲基化的2,6-脱水醛糖甲苯磺酰with与芳基卤化物的交叉偶联。反应以11-75％的收率得到了相应的芳基取代的外二糖作为非对映异构体的混合物。转化代表了对这些类型的拟糖化合物的新途径。一些芳基取代的外糖基的双键被饱和，以得到良好的苄基C-糖基衍生物的产率。