allyl 2,3,4-tri-O-benzyl-α-L-fucopyranoside | 250691-62-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl 2,3,4-tri-O-benzyl-α-L-fucopyranoside
• 英文别名: allyl 2,3,4-tri-O-benzyl-6-deoxy-α-L-galactopyranoside；(2S,3R,4R,5S,6R)-2-methyl-3,4,5-tris(phenylmethoxy)-6-prop-2-enoxyoxane
• CAS: 250691-62-4
• 化学式: C₃₀H₃₄O₅
• 分子量: 474.597
• InChiKey: GJRZTGOFUKVYMR-VGYFXUJXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  allyl 2,3,4-tri-O-benzyl-α-L-fucopyranoside 在 potassium tert-butylate 、 碘 、 碳酸氢钠 作用下， 以 四氢呋喃 、 水 、 二甲基亚砜 为溶剂， 反应 4.25h， 生成 2,3,4-tri-O-benzyl-α-L-fucopyranose
  参考文献：
  名称：

  Synthesis, NMR and Conformational Studies of Fucoidan Fragments 1:¹Desulfated 2,3- and 3,4-Branched Trisaccharide Fragments and Constituting Disaccharides

  摘要：

  Two fucotriosides with vicinal disubstitution alpha -L-Fuc-(1-->2)[alpha -L-Fuc-(1-->3)[alpha -L-Fuc-OPr (1) and alpha -L-Fuc-(1-->3)[alpha -L-Fuc-(1-->4)]alpha -L-Fuc-OPr (2), which are related to fragments of natural polysaccharides fucoidans, have been synthesized together with constituent disaccharides 3-5, Spectral and conformational properties of tri- and disaccharides have been investigated by (1)H, (13)C and NOE NMR spectroscopy.

  DOI：

  10.1080/07328300008544140
• 作为产物：
  描述：

  1-O-acetyl-2,3,4-tri-O-benzyl-L-fucopyranose 在 碘代三甲硅烷 、 4 A molecular sieve 、 四丁基碘化铵 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 allyl 2,3,4-tri-O-benzyl-α-L-fucopyranoside
  参考文献：
  名称：

  糖基碘化物在中性条件下是高效的供体

  摘要：

  摘要制备了糖基碘化物并在中性条件下进行糖基化。该反应是高效的，即使具有空间上要求的糖基受体也能得到α糖苷。葡萄糖基碘与烯丙醇的反应最慢，需要回流条件。半乳糖基碘化物是反应性的中间产物，在室温下3小时内可提供烯丙基糖苷，而岩藻糖基碘化物的糖基化在相似条件下可在不到1小时内发生。用包括异头羟基在内的各种受体证明了反应的范围和局限性，得到了海藻糖类似物。在不存在C-2参与的情况下，只需将溶剂从苯改成乙腈就可以实现葡萄糖基碘化物的β-选择性糖基化。

  DOI：

  10.1016/s0008-6215(99)00146-9

文献信息

• Sweet (hetero)aromatics: glycosylated templates for the construction of saccharide mimetics
  作者：Christine Wiebe、Claudine Schlemmer、Stefan Weck、Till Opatz

  DOI：10.1039/c1cc13078a

  日期：——

  Mono- and diglycosylated aromatics and heteroaromatics may serve as building blocks for the construction of metabolically stable mimetics of oligosaccharides. Methods for their preparation from monosaccharidic precursors by direct C-glycosylation, dipolar cycloaddition or Larock cyclization are described.

  单糖基和二糖基修饰的芳香化合物和杂芳香化合物可作为构建代谢稳定的低聚糖模拟物的砌块。本文描述了通过直接C-糖基化、偶极环加成或Larock环化反应从单糖前体合成这些化合物的方法。
• Toward the Chemical Syntheses of Fucosylated Peptides: A Combination of Protecting Groups for the Hydroxy Groups of Fucose
  作者：Yuya Asahina、Tatsuya Ando、Hironobu Hojo

  DOI：10.1246/bcsj.20220037

  日期：2022.8.15

  A combination of protecting groups for the hydroxy groups of fucose is presented. Notably, this combination enables the synthesis of glycopeptides containing acid-sensitive fucose. The relationship between the design of the protecting groups for the alcohols of fucose and the acid stability of the fucosidic linkage is elucidated. The hydrolysis of pseudo-glycopeptides incorporating various fucose-alcohol-protecting groups is investigated in a trifluoroacetic acid cocktail. The nature of the protecting group significantly affected the acid stability of the fucosidic bond, with a combination of 4-methylbenzyl and levulinoyl groups offering optimal protection of the fucosidic bond. These protecting groups were employed to realize the practical synthesis of glycopeptides containing fucose. To demonstrate the usefulness of this protecting group combination, a model octapeptide was synthesized by 9-fluorenylmethoxycarbonyl solid-phase peptide synthesis. The decomposition of the fucosidic linkage during the final deprotection of solid-phase peptide synthesis was prevented, yielding the desired fucosylated peptide. Finally, the remaining levulinoyl group was removed by hydrazine under neutral conditions to give the fully deprotected glycopeptide.

  本文介绍了用于保护岩藻糖羟基的基团组合。值得注意的是，这种组合能够合成含有对酸敏感的岩藻糖的糖肽。本文阐明了岩藻糖醇保护基团的设计与岩藻糖苷键的酸稳定性之间的关系。在一种三氟乙酸混合物中研究了含有各种岩藻糖醇保护基团的假糖肽的水解。保护基团的性质显著影响了岩藻糖苷键的酸稳定性，其中4-甲基苄基和乙酰基的组合为岩藻糖苷键提供了最佳保护。这些保护基团被用于实现含有岩藻糖的糖肽的实际合成。为了证明这种保护基团组合的有效性，通过9-芴甲氧羰基固相肽合成法合成了八肽模型。固相肽合成法在最终脱保护过程中岩藻糖苷键的分解被阻止，从而产生了所需的岩藻糖肽。最后，在中性条件下用肼除去剩余的乙酰基，得到完全脱保护的糖肽。
• Glycosyl iodides. History and recent advances
  作者：Peter J. Meloncelli、Alan D. Martin、Todd L. Lowary

  DOI：10.1016/j.carres.2009.02.032

  日期：2009.6

  The use of glycosyl iodides as an effective method for the preparation of glycosides has had a recent resurgence in carbohydrate chemistry, despite its early roots in which these species were believed to be of limited use. Renewed interest in these species as glycosylating agents has been spurred by their demonstrated utility in the stereoselective preparation of O-glycosides, and other glycosylic compounds. This review provides a brief historical account followed by an examination of the use of glycosyl iodides in the synthesis of oligosaccharicles and other glycomimetics, including C-glycosylic compounds, glycosyl azides and N-glycosides. (C) 2009 Elsevier Ltd. All rights reserved.
• Glycosyl iodides are highly efficient donors under neutral conditions
  作者：Michael J. Hadd、Jacquelyn Gervay

  DOI：10.1016/s0008-6215(99)00146-9

  日期：1999.7

  Abstract Glycosyl iodides have been prepared and subjected to glycosylation under neutral conditions. The reactions are highly efficient, giving α glycosides even with sterically demanding glycosyl acceptors. Glucosyl iodides react with allyl alcohol slowest and require refluxing conditions. Galactosyl iodides are intermediate in reactivity, providing the allyl glycoside in 3 h at room temperature

  摘要制备了糖基碘化物并在中性条件下进行糖基化。该反应是高效的，即使具有空间上要求的糖基受体也能得到α糖苷。葡萄糖基碘与烯丙醇的反应最慢，需要回流条件。半乳糖基碘化物是反应性的中间产物，在室温下3小时内可提供烯丙基糖苷，而岩藻糖基碘化物的糖基化在相似条件下可在不到1小时内发生。用包括异头羟基在内的各种受体证明了反应的范围和局限性，得到了海藻糖类似物。在不存在C-2参与的情况下，只需将溶剂从苯改成乙腈就可以实现葡萄糖基碘化物的β-选择性糖基化。
• Synthesis, NMR and Conformational Studies of Fucoidan Fragments 1:¹Desulfated 2,3- and 3,4-Branched Trisaccharide Fragments and Constituting Disaccharides
  作者：Elena A. Khatuntseva、Nadezhda E. Ustuzhanina、Georgij V. Zatonskii、Alexander S. Shashkov、Anatoly I. Usov、Nikolay E. Nifant'ev

  DOI：10.1080/07328300008544140

  日期：2000.1.1

  Two fucotriosides with vicinal disubstitution alpha -L-Fuc-(1-->2)[alpha -L-Fuc-(1-->3)[alpha -L-Fuc-OPr (1) and alpha -L-Fuc-(1-->3)[alpha -L-Fuc-(1-->4)]alpha -L-Fuc-OPr (2), which are related to fragments of natural polysaccharides fucoidans, have been synthesized together with constituent disaccharides 3-5, Spectral and conformational properties of tri- and disaccharides have been investigated by (1)H, (13)C and NOE NMR spectroscopy.