2,6-anhydro-1-deoxy-3,4,5,7-tetrakis-O-(triethylsilyl)-D-gluco-hept-1-enitol | 105539-34-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,6-anhydro-1-deoxy-3,4,5,7-tetrakis-O-(triethylsilyl)-D-gluco-hept-1-enitol
• 英文别名: 3,4,5,7-tetrakis-O-(triethylsilyl)-2,6-anhydro-1-deoxy-D-glucono-hept-1-enitol；3,4,5,7-tetra-O-triethylsilyl-2,6-anhydro-1-deoxy-D-gluco-hept-1-enitol；triethyl-[(2R,3R,4S,5R)-6-methylidene-4,5-bis(triethylsilyloxy)-2-(triethylsilyloxymethyl)oxan-3-yl]oxysilane
• CAS: 105539-34-2
• 化学式: C₃₁H₆₈O₅Si₄
• 分子量: 633.22
• InChiKey: BVGVPKFIZJQXJY-YXOGWZJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.09
• 重原子数：
  40
• 可旋转键数：
  21
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,6-anhydro-1-deoxy-3,4,5,7-tetrakis-O-(triethylsilyl)-D-gluco-hept-1-enitol 在 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 44.0h， 生成 (5R,7R,8R,9S,10R)-8,9,10-tris(acetoxy)-7-[(acetoxy)methyl]-3-(4-methoxyphenyl)-1,6-dioxa-2-azaspiro[4,5]dec-2-ene
  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：

  三乙基氯硅烷 在 咪唑 、 二氯二茂钛 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 115.0h， 生成 2,6-anhydro-1-deoxy-3,4,5,7-tetrakis-O-(triethylsilyl)-D-gluco-hept-1-enitol
  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

• Synthesis of Methylene Exoglycals Using a Modified Julia Olefination
  作者：David Gueyrard、Rose Haddoub、Amine Salem、Nassib Said Bacar、Peter G. Goekjian

  DOI：10.1055/s-2005-862364

  日期：——

  A new route to exomethylene sugars is reported. The use of a two-step coupling-elimination procedure allows successful Julia olefination of sugar-derived lactones.

  报道了外亚甲基糖的新途径。使用两步耦合消除程序可以成功实现糖衍生内酯的 Julia 烯化。
• Carbohydrate-based spiro bis(isoxazolines): synthesis and evaluation in asymmetric catalysis
  作者：David Goyard、Susanne M. Telligmann、Catherine Goux-Henry、Mike M.K. Boysen、Eric Framery、David Gueyrard、Sébastien Vidal

  DOI：10.1016/j.tetlet.2009.11.028

  日期：2010.1

  Two carbohydrate-based spiro bis(isoxazolines) were synthesized via 1,3-dipolar cycloaddition from peracetylated methylene exo-glucal and the corresponding bis(arylnitrile oxide). The bis(cycloadducts) were then evaluated as ligands for enantioselective catalytic reactions. The Pd-catalyzed Tsuji-Trost reaction between a malonate and an allylic acetate did not provide good results. The poor conversion observed can be attributed to the rearrangement of the ligand in the reaction mixture to afford the corresponding ring-opened isoxazole which has been characterized. Both ligands were also evaluated in Cu(I)-catalyzed asymmetric imine alkynylation and afforded the product in good yield and modest enantioselectivity. (C) 2009 Elsevier Ltd. All rights reserved.
• 1-Methylene sugars as C-glycoside precursors
  作者：T. V. RajanBabu、G. S. Reddy

  DOI：10.1021/jo00376a088

  日期：1986.12
• Glucose-based spiro-isoxazolines: A new family of potent glycogen phosphorylase inhibitors
  作者：Mahmoud Benltifa、Joseph M. Hayes、Sébastien Vidal、David Gueyrard、Peter G. Goekjian、Jean-Pierre Praly、Gregory Kizilis、Costas Tiraidis、Kyra-Melinda Alexacou、Evangelia D. Chrysina、Spyros E. Zographos、Demetres D. Leonidas、Georgios Archontis、Nikos G. Oikonomakos

  DOI：10.1016/j.bmc.2009.08.060

  日期：2009.10

  A series of glucopyranosylidene-spiro-isoxazolines was prepared through regio- and stereoselective [3+2]-cycloaddition between the methylene acetylated exo-glucal and aromatic nitrile oxides. The deprotected cycloadducts were evaluated as inhibitors of muscle glycogen phosphorylase b. The carbohydrate-based family of five inhibitors displays K(i) values ranging from 0.63 to 92.5 microM. The X-ray structures of the enzyme-ligand complexes show that the inhibitors bind preferentially at the catalytic site of the enzyme retaining the less active T-state conformation. Docking calculations with GLIDE in extra-precision (XP) mode yielded excellent agreement with experiment, as judged by comparison of the predicted binding modes of the five ligands with the crystallographic conformations and the good correlation between the docking scores and the experimental free binding energies. Use of docking constraints on the well-defined positions of the glucopyranose moiety in the catalytic site and redocking of GLIDE-XP poses using electrostatic potential fit-determined ligand partial charges in quantum polarized ligand docking (QPLD) produced the best results in this regard.
• Stereoselective Palladium-Catalyzed Arylation of <i>Exo</i>-Glycals with Aryl Iodides
  作者：Jeffery Regier、Supriya Ghanty、Yuri Bolshan

  DOI：10.1021/acs.joc.1c02533

  日期：2022.1.7

  A novel methodology for the arylation of exo-glycals has been developed. A range of exo-glycals underwent reactions with aryl iodides in the presence of a palladium catalyst. The transformation proceeded in a stereoselective manner to afford Z-isomers. The developed transformation demonstrated excellent functional group tolerance.

  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。