phenyl 4,6-O-benzylidene-β-D-glucopyranoside | 54502-82-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 4,6-O-benzylidene-β-D-glucopyranoside
• 英文别名: Phenyl 4,6-O-benzylidene-b-D-glucopyranoside；(4aR,6S,7R,8R,8aS)-6-phenoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-7,8-diol
• CAS: 54502-82-8
• 化学式: C₁₉H₂₀O₆
• 分子量: 344.364
• InChiKey: VEVONSHXUHYXKX-HIQCEYAYSA-N

物化性质

• 熔点：
  194.5-195 °C
• 沸点：
  556.2±50.0 °C(Predicted)
• 密度：
  1.328±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 4,6-O-benzylidene-β-D-glucopyranoside 在 erbium(III) triflate 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以78%的产率得到苯基-BETA-葡萄糖吡喃糖苷
  参考文献：
  名称：

  使用三氟甲磺酸（（III）裂解亚苄基乙缩醛的温和有效方法。

  摘要：

  在亚苄基衍生物的温和脱保护方案中，提出了Er（OTf）3作为新型有效的路易斯酸催化剂。在改进的方法中，其中使用乙酸酐作为反应溶剂，可以定量收率和非常短的反应时间实现亚苄基乙缩醛的同时裂解和底物的过乙酰化。

  DOI：

  10.1039/b511314h
• 作为产物：
  描述：

  苯甲醛二甲缩醛 、 苯基-BETA-葡萄糖吡喃糖苷 在 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以97%的产率得到phenyl 4,6-O-benzylidene-β-D-glucopyranoside
  参考文献：
  名称：

  环状磷酸酯寡糖：新型环状寡糖类似物的合成和构象行为

  摘要：

  CyPLOS（环状磷酸酯连接的寡糖），即由两个，三个和四个通过稳定的磷酸二酯键连接的4,6-苯基-β - d-吡喃葡萄糖苷单元组成的新型环状寡糖替代物，是通过直接和简单的方法制备的有效的固相协议。线性前体的组装是通过标准的亚磷酰胺化学方法在自动化的DNA合成仪上进行的，其中使用了适当保护的d的4-亚磷酰胺衍生物-葡萄糖为基础。对于关键的环化步骤，采用了磷酸三酯方法，然后进行温和的碱性处理，以高纯度的形式在溶液中释放出所需的环状分子。环状二聚体和三聚体也可以通过经典的溶液合成方法独立地制备，基本上遵循相同的方法。还报道了通过详细的NMR分析获得的环状二聚体和三聚体的溶液结构偏好。

  DOI：

  10.1021/jo0600757

文献信息

• Synthesis, extraction ability and application in asymmetric synthesis of azacrown ethers derived from D-glucose
  作者：Péter Bakó、Kristóf Vízvárdi、Suzanne Toppet、Erik Van der Eycken、Georges J. Hoornaert、László Tõke

  DOI：10.1016/s0040-4020(98)00938-7

  日期：1998.12

  A number of new chiral monoaza-15-crown-5 derivatives (4–9) and lariat ethers (10–15) anellated to phenyl-β-D-glucopyranoside have been synthesized. Their extracting ability was measured with alkali metal (Li, Na, K) and ammonium cations. The derivatives show significant asymmetric induction as phase transfer catalysts in the Michael addition of 2-nitropropane to chalcone (82% ee) although in low yield

  合成了许多新的手性单氮杂15冠5衍生物（4-9）和环烷基苯-β-D-吡喃葡萄糖苷的套索状醚（10-15）。用碱金属（Li，Na，K）和铵阳离子测量它们的萃取能力。该衍生物显示出显着的不对称诱导作用，这是尽管将2-硝基丙烷的迈克尔加成到查尔酮中（82％ee），但收率低，并且在苯甲酰氯与苯甲醛的Darzens缩合中（74％ee）显示出明显的不对称诱导。冠醚的氮原子上的取代基对萃取能力和对映选择性均具有重大影响。
• Simple and efficient MW-assisted cleavage of acetals and ketals in pure water
  作者：Antonio Procopio、Marco Gaspari、Monica Nardi、Manuela Oliverio、Antonio Tagarelli、Giovanni Sindona

  DOI：10.1016/j.tetlet.2007.10.038

  日期：2007.12

  Simple and efficient MW-assisted cleavage of acetal and ketal is proposed in deionized water and in a very short time.

  提出了在去离子水中并在很短的时间内简单有效地进行MW辅助的乙缩醛和缩酮的裂解。
• Synthesis of deoxy and acylamino derivatives of lactose and use of these for probing the active site of Neisseria meningitidis N-acetylglucosaminyltransferase
  作者：Ulrika Westerlind、Per Hagback、Björn Tidbäck、Lotta Wiik、Ola Blixt、Nahid Razi、Thomas Norberg

  DOI：10.1016/j.carres.2004.11.017

  日期：2005.2

  Derivatives of lactose with the galactose ring substituents replaced by deoxy or acylamino functions were prepared. The 2'-, 3'-. 4'- and 6'-deoxy, 3'-acetamido and 3'-benzamido derivatives of phenyl 4-O-(beta-D-galactopyranosyl)-beta-D-glucopyranoside (phenyl P-lactoside) were synthesized from disaccharide or monosaccharide precursors. The derivatives were tested as substrates for the N-acetylglucosaminyltransferase from Neisseria meningitidis, which uses lactosyl derivatives as acceptors and UDP-GlcNAc as the donor in a beta-(1-->3) glycosylation reaction. The 6'-deoxy derivative was nearly threefold as active as phenyl beta-lactoside, whereas the 2'- and 4'-deoxy derivatives were less active. The other derivatives were inactive, as expected. (C) 2004 Elsevier Ltd. All rights reserved.
• Synthesis of novel HIV-1 protease inhibitors based on carbohydrate scaffolds
  作者：Paul V Murphy、Julie L O'Brien、Lorraine J Gorey-Feret、Amos B Smith

  DOI：10.1016/s0040-4020(03)00208-4

  日期：2003.3

  The synthesis of peptidomimetic inhibitors of HIV-1 protease based on 6-deoxy-6-aniino-beta-D-glucopyranoside and 6-deoxy-6-amino- beta-D-mannopyranoside scaffolds has been achieved. The inhibitors had IC50 values in the micromolar range. The results provide a platform for the development of more potent carbohydrate based inhibitors of HIV-1 and other aspartic proteases. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Carbohydrate Phosphinites as Practical Ligands in Asymmetric Catalysis:  Electronic Effects and Dependence of Backbone Chirality in Rh-Catalyzed Asymmetric Hydrogenations. Synthesis of <i>R</i>- or <i>S</i>-Amino Acids Using Natural Sugars as Ligand Precursors
  作者：T. V. RajanBabu、Timothy A. Ayers、Gary A. Halliday、Kimberly K. You、Joseph C. Calabrese

  DOI：10.1021/jo970884d

  日期：1997.8.1

  Vicinal diarylphosphinites derived from carbohydrates are excellent ligands for the Rh(I)-catalyzed enantioselective asymmetric hydrogenation of dehydroamino acid derivatives, producing the highest enantioselectivity of any ligands directly prepared from natural products. The enantioselectivity can be enhanced by the appropriate choice of substituents on the aromatic rings of the phosphinites. For example, the use of phosphinites with electron-donating bis(3,5-dimethylphenyl) groups on phosphorus provides ee's up to 99% for a wide range of amino acids including some with easily removable N-protecting groups. Electron-withdrawing aryl substituents, on the other hand, decrease the enantioselectivity. Sense of chiral induction in the amino acid product depends on the relative juxtaposition of the vicinal diphosphinites on a given sugar backbone. When readily available D-glucopyranosides are used as the starting sugars, 2,3-phosphinites give the S-amino acids and 3,4-phosphinites give the R-amino acids. In the case of aromatic and heteroaromatic amino acids, enantioselectivities > 95% are consistently obtained. Practical considerations such as the ease of ligand synthesis, rates of reactions, catalyst turnover, and scope and limitations in terms of substrates are discussed. A possible explanation for the enhancement of enantioselectivity by electron-rich phosphinites is offered.