1,3,4,6-四-o-乙酰基-alpha-d-吡喃半乳糖 | 19186-40-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 1,3,4,6-四-o-乙酰基-alpha-d-吡喃半乳糖
• 英文名称: 1,3,4,6-tetra-O-acetyl-α-D-galactopyranoside
• 英文别名: 1,3,4,6-tetra-O-acetyl-α-D-galactopyranose；1,3,4,6-tetra-O-acetyl-alpha-D-galactopyranose；[(2R,3S,4R,5R,6R)-3,4,6-triacetyloxy-5-hydroxyoxan-2-yl]methyl acetate
• CAS: 19186-40-4
• 化学式: C₁₄H₂₀O₁₀
• 分子量: 348.307
• InChiKey: SHBHJRVMGYVXKK-RGDJUOJXSA-N

物化性质

• 熔点：
  138-140°C
• 沸点：
  160-170 °C(Press: 0.01 Torr)
• 密度：
  1.33±0.1 g/cm3(Predicted)
• 溶解度：
  溶于氯仿、乙酸乙酯、甲醇

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  135
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1,3,4,6-四-o-乙酰基-alpha-d-吡喃半乳糖 在 2,4,6-三甲基吡啶 、 1,1-二氯甲醚 、 sodium methylate 、 silver trifluoromethanesulfonate 、 silver perchlorate 、 zinc(II) chloride 作用下， 以 乙醚 、 二氯甲烷 、 氯仿 、 甲苯 为溶剂， 反应 17.75h， 生成 α-L-Rhap-(1[*]2)-α-D-GalpOMe
  参考文献：
  名称：

  Synthesis of ligands related to the O-specific antigen of type 1 Shigella dysenteriae. 3. Glycosylation of 4,6-O-substituted derivatives of methyl 2-acetamido-2-deoxy-.alpha.-D-glucopyranoside with glycosyl donors derived from mono- and oligosaccharides.

  摘要：

  Methyl O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranoside, obtained by silver trifluoromethanesulfonate-mediated condensation of methyl 2,4-di-O-benzoyl-alpha-L-rhamnopyranoside and 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl bromide (3), was cleaved with dichloromethyl methyl ether (DCMME) to give O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranosyl chloride (9). Condensations of 1,3,4,6-tetra-O-acetyl-alpha-D-galactopyranose with 3 and 9, followed by treatment of the products with DCMME yielded, respectively, glycosyl chlorides 12 and 17. Each of these, as well as 2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl chloride was condensed with 4,6-O-substituted (benzylidene, tetraisopropyl-disiloxane-1,3-diyl, or benzyl) derivatives of methyl 2-acetamido-2-deoxy-alpha-D-glucopyranoside, using CH2Cl2, ether, or a mixture thereof as the solvent. The formation of the desired alpha-D-galactopyranosyl linkage was favored when ether was the solvent. Under these conditions, however, the combined yield of the condensation products decreased, especially when less reactive synthons were used. The alpha-linked products obtained were deprotected to give the methyl alpha-glycosides of the tetra, tri-, and the disaccharide related to the chemical repeating unit of the O-specific side chain of the lipopolysaccharide of Shigella dysenteriae type 1. Synthesis of methyl alpha-glycosides of three other constituents of the same polymeric antigen [alpha-L-Rha-(1 --> 3)-alpha-L-Rha, alpha-L-Rha-(1 --> 2)-alpha-D-Gal, and alpha-L-Rha-(1 --> 3)-alpha-L-Rha-(1 --> 2)-alpha-D-Gal] are also described.

  DOI：

  10.1021/jo00034a047
• 作为产物：
  描述：

  beta-D-半乳糖五乙酸酯 在 水 、 三氟乙酸 作用下， 反应 5.0h， 以70%的产率得到1,3,4,6-四-o-乙酰基-alpha-d-吡喃半乳糖
  参考文献：
  名称：

  Stereoselective synthesis of α-L-Fucp-(1,2)- and -(1,3)-β-D-Galp(1)-4-methylumbelliferone using glycosyl donor substituted by propane-1,3-diyl phosphate as leaving group

  摘要：

  合成双糖α-L-岩藻糖-(1,2)-和α-L-岩藻糖-(1,3)-β-D-半乳糖-(1)-4-甲基伞花素作为岩藻糖苷酶底物，通过用TMSOTf激活2,3,4-三-O-乙酰基和2,3,4,6-四-O-乙酰基α,β-L-岩藻糖和-D-半乳糖基丙烷-1,3-二醇磷酸盐的异头中心，并对4-甲基伞花素β-D-半乳糖苷进行了最小保护。

  DOI：

  10.1039/b002754p

文献信息

• Assembly of a Complex Branched Oligosaccharide by Combining Fluorous-Supported Synthesis and Stereoselective Glycosylations using Anomeric Sulfonium Ions
  作者：Wei Huang、Qi Gao、Geert-Jan Boons

  DOI：10.1002/chem.201501844

  日期：2015.9.7

  reliable strategies for the rapid assembly of complex oligosaccharides. This paper presents a set of strategically selected orthogonal protecting groups, glycosyl donors modified by a (S)‐phenylthiomethylbenzyl ether at C‐2, and a glycosyl acceptor containing a fluorous tag, which makes it possible to rapidly prepare complex branched oligosaccharides of biological importance. The C‐2 auxiliary controlled

  迫切需要开发可靠的策略来快速组装复杂的寡糖。本文提出了一组战略性选择的正交保护基团、C-2 处 ( S )-苯硫基甲基苄基醚修饰的糖基供体以及含有氟标签的糖基受体，这使得快速制备具有生物学重要性的复杂支链寡糖成为可能。C-2辅助剂控制各种半乳糖基化的1,2-顺式异头选择性。正交保护基团2-萘甲基醚（Nap）和乙酰丙酸酯（Lev）使得生成糖基受体并允许安装拥挤的支化点成为可能。糖基化后，可以使用酸性条件去除手性辅助剂，这与正交保护基团 Lev 和 Nap 的存在相容，从而可以有效安装 1,2 连接糖苷。轻氟标签使得使用碳氟化合物改性的硅胶通过简单的过滤方法纯化化合物成为可能。该组构件已成功用于制备布氏锥虫 GPI 锚的碳水化合物部分，该寄生虫是一种导致人类昏睡病和家畜类似疾病的寄生虫。
• Neighboring Group Participation in Glycosylation Reactions by 2,6-Disubstituted 2-<i>O</i>-Benzoyl groups: A Mechanistic Investigation
  作者：Rohan J. Williams、Nathan W. McGill、Jonathan M. White、Spencer J. Williams

  DOI：10.1080/07328303.2010.508141

  日期：2010.7.1

  Variable yields and glycosylation stereoselectivity were obtained for NIS/TfOH-medi- ated reaction of 4-methoxyphenyl 2,4,6-tetra-O-acetyl-β-D-galactopyranoside and thiogalactosides bearing acetyl, benzoyl, 2,6-dimethoxylbenzoyl, 2,4,6-trimethylbenzoyl, or 2,6-dichlorobenzoyl groups at the 2-positions and acetyl at the remainder. X-ray structures of 4-methylphenyl 2,3,4,6-tetra-O-(2,4,6-trimethylb

  对于NIS / TfOH介导的4-甲氧基苯基2,4,6-四-O-乙酰基-β-D-吡喃半乳糖苷和带有乙酰基，苯甲酰基，2,6-二甲氧基苯甲酰基的硫代半乳糖苷的反应，获得了不同的收率和糖基化立体选择性。在2-位的是2,4,6-三甲基苯甲酰基或2,6-二氯苯甲酰基，其余为乙酰基。4-甲基苯基2,3,4,6-四的X射线结构Ö - （2,4,6-三甲基苯甲酰）-1-硫代β-d-galactopyr anoside和4-甲基苯基3,4- ø -异亚丙基-2,6-二-O-（2,4,6-三甲基苯甲酰基）-1-硫代-β-D-吡喃半乳糖苷显示轻微扭曲的4 C 1椅子构象。可变温度NMR显示4-甲基苯基2,3,4,6-tetra- O的活化-（2,4,6-三甲基苯甲酰基）-1-硫代-β-D-吡喃半乳糖苷仅提供二恶唑鎓离子，而4-甲基苯基3,4,6-三-O-乙酰基-2- O-（2,4， 6-三甲基苯甲酰基）-1-
• Linear Synthesis of a Protected H-Type II Pentasaccharide Using Glycosyl Phosphate Building Blocks
  作者：Kerry Routenberg Love、Rodrigo B. Andrade、Peter H. Seeberger

  DOI：10.1021/jo015987h

  日期：2001.11.1

  a variety of nitrogen protecting groups to ensure good glucosamine donor reactivity and protecting group compatibility. The challenge to differentiate C2 of the terminal galactose in the presence of other hydroxyl and amine protecting groups prompted us to introduce the 2-(azidomethyl)benzoyl group as a novel mode of protection for carbohydrate synthesis. The compatibility of this group with traditionally

  报道了利用糖基磷酸酯和糖基三氯乙酰亚氨酸酯结构单元线性合成完全受保护的H型II血型决定子五糖。设想了血型决定簇的自动固相合成，已证明糖基磷酸酯在逐步构建复杂的寡糖（例如H型II型抗原）中的效用。中央氨基葡萄糖结构单元的安装要求筛选各种氮保护基，以确保良好的氨基葡萄糖供体反应性和保护基的相容性。在存在其他羟基和胺保护基的情况下，区分末端半乳糖的C2的挑战促使我们引入2-（叠氮甲基）苯甲酰基作为碳水化合物合成的新型保护方式。检查了该基团与传统使用的保护基的相容性，以及其在糖基化中作为C2立体定向基团的用途。2-（叠氮甲基）苯甲酰基的应用以及对糖基供体的系统评价允许五糖的完成，并提供了预期普遍适用于血型决定簇的固相支持体合成的合成策略。
• Stereoselective Ring-Opening of Acetylated Pyranose-1,2-(etyl orthoacetates).
  作者：Setsuo SAITO、Shigeya SUMITA、Koki ICHINOSE、Yasuhiko KANDA

  DOI：10.1248/cpb.41.90

  日期：——

  When acetylated pyranose-1, 2-(ethyl orthyl orthoacetates) were hydrolyzed in acidic solvents, the ring-opening of the orthoacetate rings was influenced by the axial or equatorial OAc group at C-4 on the pyranoses; on acid-catalyzed hydrolysis, 3, 4, 6-tri-O-acetyl-α-D-glactopyranose- (8) and methyl 3, 4-di-O-acetyl-α-D-galacturonatopyranose-1, 2-(ethyl orthoacetate) (16) having an axial OAc group at C-4 on the pyranose rings gave 1, 3, 4, 6-tetra-O-acetyl-α-D-galactopyranose (9) and methyl 1, 3, 4-tri-O-acetyl-α-D-galacturonatopyranose (23), respectively, whereas 3, 4, 6-tri-O-acetyl-α-D-glucopyranose- (10) and methyl 3, 4-di-O-acetyl-α-D-glucuronatopyranose-1, 2-(ethyl orthoacetate) (22)having an equatorial OAc group at C-4 on the pyranose rings gave 2, 3, 4, 6-tetra-O-acetyl-D-glucopyranose (11) and methyl 2, 3, 4-tri-O-acetyl-D-glucuronatopyranose (24), respectively. On the acid-catalyzed hydrolysis, 3, 4-di-O-acetyl-β-L-arabinopyranose-1, 2-(ethyl orthoacetate) (34) having an axial OAc group at C-4 on the pyranose ring gave a mixture of 1, 3, 4-tri-O-acetyl-β-L- (35) and 2, 3, 4-tri-O-acetyl-L-arabinopyranose (36). These selectivities of ring-opening of the 1, 2-(orthoacetates) were considered to have resulted from the differences of the conformers fo the 1, 2-(orthoacids)intermediates derived from the 1, 2-(othoacetates) and the orientation of the acetyl groups at C-4 on the pyranose rings.

  当乙酰化的吡喃糖1,2-(乙基邻酸酯)在酸性溶剂中水解时，邻酸酯环的开环受吡喃糖C-4位点的轴向或赤道OAc基团的影响；在酸催化水解过程中，具有C-4轴向OAc基团的3,4,6-三-O-乙酰-α-D-半乳糖吡喃糖-(8)和甲基3,4-二-O-乙酰-α-D-半乳糖酸吡喃糖-1,2-(乙基邻酸酯)(16)分别生成1,3,4,6-四-O-乙酰-α-D-半乳糖吡喃糖(9)和甲基1,3,4-三-O-乙酰-α-D-半乳糖酸吡喃糖(23)，而具有C-4赤道OAc基团的3,4,6-三-O-乙酰-α-D-葡萄糖吡喃糖-(10)和甲基3,4-二-O-乙酰-α-D-葡萄糖醛酸吡喃糖-1,2-(乙基邻酸酯)(22)则分别生成2,3,4,6-四-O-乙酰-D-葡萄糖吡喃糖(11)和甲基2,3,4-三-O-乙酰-D-葡萄糖醛酸吡喃糖(24)。在酸催化水解过程中，具有C-4轴向OAc基团的3,4-二-O-乙酰-β-L-阿拉伯糖吡喃糖-1,2-(乙基邻酸酯)(34)生成1,3,4-三-O-乙酰-β-L-(35)和2,3,4-三-O-乙酰-L-阿拉伯糖吡喃糖(36)的混合物。这些1,2-(邻酸酯)的开环选择性被认为是由1,2-(邻酸)中间体的构象差异以及吡喃糖环上C-4位置的乙酰基团的取向所导致的。
• Stereoselective 1,2-cis-galactosylation assisted by remote neighboring group participation and solvent effects
  作者：Alexei V. Demchenko、Emmanuel Rousson、Geert-Jan Boons

  DOI：10.1016/s0040-4039(99)01203-4

  日期：1999.9

  Iodonium-ion promoted glycosylations in 1,4-dioxane/toluene with galactosyl donors having an electron-donating neighboring group participating functionality at C-4 give exceptional high α-anomeric selectivities.

  碘鎓离子在1,4-二恶烷/甲苯中促进的糖基化反应以及在C-4上具有供电子的邻近基团参与官能团的半乳糖基供体赋予了极高的α-异头异构体选择性。