methyl 2-O-benzyl-3-O-allyl-4,6-O-benzylidene-α-D-glucopyranoside | 203717-51-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2-O-benzyl-3-O-allyl-4,6-O-benzylidene-α-D-glucopyranoside
• 英文别名: (2R,4aR,6S,7R,8S,8aR)-6-methoxy-2-phenyl-7-phenylmethoxy-8-prop-2-enoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• CAS: 203717-51-5
• 化学式: C₂₄H₂₈O₆
• 分子量: 412.483
• InChiKey: FKGPXCORSJGLIC-XOJBGPSCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2-O-benzyl-3-O-allyl-4,6-O-benzylidene-α-D-glucopyranoside 在 三乙基硅烷 、 碘 作用下， 以 乙腈 为溶剂， 反应 0.17h， 以88%的产率得到methyl 2,6-di-O-benzyl-3-O-allyl-α-D-glucopyranoside
  参考文献：
  名称：

  使用三乙基硅烷和碘对亚苄基缩醛进行区域选择性还原开环

  摘要：

  已经开发了新的反应条件，用于使用三乙基硅烷和分子碘对碳水化合物衍生物中的亚苄基缩醛进行区域选择性还原开环。反应速度快，与寡糖合成中遇到的大多数官能团相容，产率极好。反应条件在硫糖苷中同样有效。

  DOI：

  10.1055/s-0029-1219798
• 作为产物：
  描述：

  4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 在 sodium hydride 、 二正丁基氧化锡 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 2-O-benzyl-3-O-allyl-4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of 1-0-[(3S,4R)-3-hydroxytetrahydrofuran-4-yl]-α-D-glucopyranoside 3,4,3′-trisphosphate as a novel potent IP3 receptor ligand

  摘要：

  1-O-[(3S,4R)-3-Hydroxytetrahydrofuran-4-yl]-alpha-D-glucopyranoside 3,4,3'-trisphosphate (5) was designed and synthesized as a novel IP3 receptor ligand. This compound bound strongly to IP3 receptor from porcine cerebella with an affinity comparable to that of IP3. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00954-x

文献信息

• SmI₂/Water/Amine Mediates Cleavage of Allyl Ether Protected Alcohols:  Application in Carbohydrate Synthesis and Mechanistic Considerations
  作者：Anders Dahlén、Andreas Sundgren、Martina Lahmann、Stefan Oscarson、Göran Hilmersson

  DOI：10.1021/ol0354831

  日期：2003.10.1

  [reaction: see text]. SmI2/H2O/amine provides selective cleavage of unsubstituted allyl ethers in good to excellent yields. This method is therefore useful in deprotection of alcohols and carbohydrates.

  [反应：请参见文字]。SmI2 / H2O /胺可很好地至优异的收率选择性裂解未取代的烯丙基醚。因此，该方法可用于醇和碳水化合物的脱保护。
• Synthesis, NMR spectroscopy and conformational studies of the four anomeric methyl glycosides of the trisaccharide D-Glcp-(1→3)-[D-Glcp-(1→4)]-α-D-Glcp
  作者：Peter Söderman、Per-Erik Jansson、Göran Widmalm

  DOI：10.1039/a707346a

  日期：——

  The four anomeric methyl glycosides of the vicinally disubstituted trisaccharide D-Glcp-(1→3)-[D-Glcp-(1→4)]-α-D-Glcp have been synthesized using silver trifluoromethanesulfonate mediated glycosylations. The 1H and 13C NMR resonances have been assigned and used for extraction of glycosylation shifts, i.e. the differences between chemical shifts for signals from the trisaccharides and those of the respective monomers, as well as those derived by addition of the glycosylation shifts for each disaccharide element. Glycosylation shifts are up to 0.5 ppm for proton and 10 ppm for carbon. Deviations from additivity are –0.2–0.1 ppm for proton and –4.5–2.3 ppm for carbon, usually confined to the atoms at the linkage positions. The conformational space spanned for the trisaccharides, and the constituent disaccharides, has been investigated by Metropolis Monte Carlo simulations using the HSEA force field. The α-linked glucosyl groups show larger conformational changes with multiple energy minima, whereas the β-linked glucosyl groups have a single energy minimum, close to that identified for the constituent disaccharide.

  四种脱氧间位二取代的三糖D-Glcp-(1→3)-[D-Glcp-(1→4)]-α-D-Glcp的异构体甲基糖苷已通过三氟甲磺酸银催化的糖苷化反应合成。已对其1H和13C NMR谱峰进行了赋值，并用于提取糖苷化位移，即三糖信号与各自单体信号的化学位移之间的差异，以及对每个二糖单元的糖苷化位移的累加。糖苷化位移的变化范围为质子最多可达0.5 ppm，碳可达10 ppm。偏离加性规律的值则为-0.2至-0.1 ppm（质子）和-4.5至-2.3 ppm（碳），通常集中在连接位置的原子上。通过使用HSEA力场的Metropolis Monte Carlo模拟，研究了三糖及其组成的二糖所涵盖的构象空间。α-链接的葡萄糖基显示出较大的构象变化和多个能量最小点，而β-链接的葡萄糖基则只有一个能量最小点，接近于其组成的二糖所识别的能量最低点。
• Exploring the Optimal Site for Modifications of Pyranmycins with the Extended Arm Approach
  作者：Jie Li、Jinhua Wang、Yu Hui、Cheng-Wei Tom Chang

  DOI：10.1021/ol027288c

  日期：2003.2.1

  [GRAPHICS]Continuing from the syntheses and the antibacterial studies of a library of pyranmycins, we further probed the proximity around ring III of pyranmycin by introducing an "extended arm" that has hydroxyethyl or aminoethyl groups at the O-2", O-3", or O-4" positions. The results from the antibacterial studies reveal the optimal structural motif is the attachment of an extended arm with a terminal hydroxyl group at the O-3" position.
• Synthesis of Adenophostin Analogues Lacking the Adenine Moiety as Novel Potent IP₃ Receptor Ligands:  Some Structural Requirements for the Significant Activity of Adenophostin A
  作者：Satoshi Shuto、Kazuya Tatani、Yoshihito Ueno、Akira Matsuda

  DOI：10.1021/jo980925l

  日期：1998.11.1

  1-O-Tetrahydrofuranyl-alpha-D-glucopyranose derivatives 5-8 were designed and synthesized as novel IP3 receptor ligands. The glycosidation reactions between fluoroglycosyl donor 23 and tetrahydrofuran derivatives 11-14 as glycosyl accepters selectively gave the corresponding alpha-glycosides, which were converted into the target Compounds 5-8 via the introduction of phosphate groups using the phosphoramidite method. Among these compounds, 1-O-tetrahydrofuranyl-alpha-D-glucopyranose trisphosphate derivatives 5 and 8 significantly inhibited the binding of [H-3] IP3 to IP3 receptor from porcine cerebella, with IC50 values of 25 and 27 nM, respectively, which were comparable to the affinity of IP3 itself.
• Regioselective Reductive Ring Opening of Benzylidene Acetals Using Triethylsilane and Iodine
  作者：Anup Misra、Rajib Panchadhayee

  DOI：10.1055/s-0029-1219798

  日期：2010.5

  Novel reaction conditions have been developed for the regioselective reductive ring opening of benzylidene acetals in carbohydrate derivatives using triethylsilane and molecular iodine. The reaction is fast, compatible with most of the functional groups encountered in the oligosaccharide synthesis, and yields were excellent. The reaction conditions are equally effective in thioglycosides.

  已经开发了新的反应条件，用于使用三乙基硅烷和分子碘对碳水化合物衍生物中的亚苄基缩醛进行区域选择性还原开环。反应速度快，与寡糖合成中遇到的大多数官能团相容，产率极好。反应条件在硫糖苷中同样有效。