2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-galactopyranoside | 189744-10-3

• 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: 2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-galactopyranoside
• 英文别名: (2S,4aR,6R,7R,8R,8aR)-2-phenyl-6-(2-trimethylsilylethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-7,8-diol
• CAS: 189744-10-3
• 化学式: C₁₈H₂₈O₆Si
• 分子量: 368.502
• InChiKey: VHVMJWGDZRGIAG-BLONOQDTSA-N

物化性质

• 沸点：
  500.4±50.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-galactopyranoside 在 盐酸 、 N-碘代丁二酰亚胺 、 molecular sieve 、 三氟甲磺酸 、 silver silicate 、 四丁基溴化铵 、 sodium hydride 、 二正丁基氧化锡 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 29.0h， 生成 2-(trimethylsilyl)ethyl 4-O-[(4-O-acetyl-2,3-di-O-benzyl-α-L-rhamnopyranosyl)-2,3-di-O-benzoyl-6-O-benzyl-β-D-glucopyranosyl]-3-O-alyl-2,6-di-O-benzyl-β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of a Single Repeat Unit of Type VIII Group BStreptococcusCapsular Polysaccharide¹

  摘要：

  We have synthesized a single repeat unit of type VIII Group B Streptococcus capsular polysaccharide, the structure of which is {L-Rhap(beta 1-->4)-D-Glcp(beta 1-->4) [Neu5Ac(alpha 2-->3)]-D-Galp(beta 1-->4}(n). The synthesis presented three significant synthetic challenges namely: the L-Rhap(beta 1-->4)-D-Glcp bond, the Neu5Ac(alpha 2-->3)-D-Galp bond and 3,4-D-Galp branching. The L-Rhap bond was constructed in 60% yield (alpha:beta l:1.2) using 4-O-acetyl-2, 3-di-O-benzoyl-alpha-L-rhamnopyranosyl bromide 6 as donor, silver silicate as promotor and 6-O-benzyl-2,3-di-O-benzoyl-1-thio-beta-D-glucopyranoside as acceptor to yield disaccharide 18. The Neu5Ac(alpha 2-->3) linkage was synthesized in 66% yield using methyl [phenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycero-D-galacto-nonulopyranosid]onate as donor and triol 2-(trimethylsilyl) ethyl 6-O-benzyl-beta-D-galactopyranoside as acceptor to give disaccharide 21. The 3,4-D-Galp branching was achieved by regioselective glycosylation of disaccharide diol 21 by disaccharide 18 in 28% yield to give protected tetrasaccharide 22. Tetrasaccharide 22 was deprotected to give as its 2-(trimethylsilyl)ethyl glycoside the title compound 1a. In addition the 2-(trimethylsilyl)ethyl group was cleaved and the tetrasaccharide coupled by glycosylation (via tetrasaccharide trichloroacetimidate) to a linker suitable for conjugation.

  DOI：

  10.1080/07328309708007324
• 作为产物：
  描述：

  苯甲醛二甲缩醛 、 2-(三甲基硅烷基)乙基beta-吡喃半乳糖苷 在 碘 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以85%的产率得到2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-galactopyranoside
  参考文献：
  名称：

  Efficient Iodine‐Catalyzed Preparation of Benzylidene Acetals of Carbohydrate Derivatives

  摘要：

  An efficient preparation of benzylidene acetals of carbohydrate derivatives catalyzed by iodine has been developed. Yields were excellent in every case.

  DOI：

  10.1080/07328300802030837

文献信息

• A Highly Convergent Synthesis of a Complex Oligosaccharide Derived from Group B Type III <i>Streptococcus</i>
  作者：Alexei V. Demchenko、Geert-Jan Boons

  DOI：10.1021/jo001477w

  日期：2001.4.1

  An efficient synthesis of a heptasaccharide derived from group B type III Streptococcus carrying an artificial spacer (1) is described. Rapid assembly of a protected heptasaccharide (16a) is accomplished from readily available building blocks 2-5 without a single protecting group manipulation between glycosylation steps. The synthetic strategy may be applied to the assembly of other branched complex

  描述了一种有效的合成带有人工间隔子（1）的B型III型链球菌衍生的七糖的方法。受保护的七糖（16a）的快速组装是从容易获得的结构单元2-5完成的，而无需在糖基化步骤之间进行单个保护基操作。合成策略可以应用于其他分支复杂寡糖的组装。将脱保护的七糖1与聚[N-（丙烯酰氧基）琥珀酰亚胺]偶联，所得物质将用于ELISA分析的开发，以检测针对孕妇的GBS III型抗体。
• A novel and versatile glycosyl donor for the preparation of glycosides of N-acetylneuraminic acid
  作者：Alexei V Demchenko、Geert-Jan Boons

  DOI：10.1016/s0040-4039(98)00359-1

  日期：1998.5

  An N-diacetyl derivative of neuraminic acid exhibits excellent glycosyl donor properties and is a very useful substrate for the preparation of glycosides of N-acetylneuraminic acid. The donor will be a key component in the preparation of a heptasaccharide derived from group B type III Streptococcus.

  一个Ñ二乙酰基衍生物神经氨酸表现出优异的糖基供体的属性和为的糖苷的制备非常有用的基板Ñ -acetylneuraminic酸。供体将是制备来自B型III型链球菌的七糖的关键组成部分。
• A stereoselective approach to phosphodiester-linked oligomers of the repeating unit of Escherichia coli K52 capsular polysaccharide containing β-D-fructofuranosyl moieties
  作者：Stefan Oscarson、Fernando W. Sehgelmeble

  DOI：10.1016/j.tetasy.2004.11.051

  日期：2005.1

  A stereoselective synthesis of a dimer, β-D-Fruf-(2→2)-α-D-Galp-(1-PO3H-3)-[β-D-Fruf-(2→2)]-D-Galp, of the repeating unit of the K52 type CPS of E. coli is described. The β-fructofuranosyl residue was introduced in a DMTST-promoted coupling using a 1,4-TIPS-bridged thiofructofuranoside donor and a 2-OH TMSE galactoside acceptor affording exclusively the β-linked disaccharide. Protecting group manipulation

  二聚体，β-d-的Fru的立体选择性合成˚F - （2→2）-α-d-Gal的p - （1-PO 3 H-3） - [β-d-的Fru ˚F - （2→2） ] -D-Gal p，是大肠杆菌K52型CPS的重复单元描述。使用1，4-TIPS桥连的硫代果糖呋喃糖苷供体和2-OH TMSE半乳糖苷受体将D-果糖呋喃糖基残基引入DMTST促进的偶联中，仅提供β-连接的二糖。该二糖的保护基操纵产生了3-OH受体和还原二糖，它们使用H-膦酸酯化学经由磷酸二酯桥连接。半缩醛仅以α-端基异构体形式存在，为什么膦酰化可以立体选择性地产生α-H-膦酸酯单酯。在3-OH二糖受体存在下用新戊酰氯活化后者，然后进行I 2-氧化，以高收率得到目标二聚体。
• Sialylations reactions: Expanding the effect of silicon protecting groups at C-4
  作者：Alexanndra Behm、Jessica Hafner、Natalie Goeckner、Matthew Lohman、Cristina De Meo

  DOI：10.1016/j.carres.2022.108707

  日期：2022.12

  goal into evaluating the effect of O-protecting groups in sialylation reactions, we compared the reactivities of phenylthio α- and β-sialyl donors protected at C-4 with tert-butyldimethyl silyl (TBDMS) and tri-isopropylsilyl (TIPS) groups in the coupling with primary and secondary galactosyl acceptors. The effect of the solvent and the donor's anomeric configuration were investigated and compared to

  作为评估O保护基团在唾液酸化反应中的影响的一般研究目标的一部分，我们比较了在 C-4 处保护的苯硫基 α- 和 β- 唾液酸供体与叔丁基二甲基甲硅烷基 (TBDMS) 和三-与初级和次级半乳糖基受体偶联的异丙基甲硅烷基 (TIPS) 基团。研究了溶剂和供体异头构型的影响，并与之前公布的数据进行了比较。事实证明，C-4 上的硅基团对唾液酸化反应有重大影响，一般而言，使用乙腈可以优化它们的整体性能。
• The First Total Synthesis of 6-Sulfo-de-N-acetylsialyl Lewisx Ganglioside: A Superior Ligand for Human L-Selectin
  作者：Shiro Komba、Christine Galustian、Hideharu Ishida、Ten Feizi、Reiji Kannagi、Makoto Kiso

  DOI：10.1002/(sici)1521-3773(19990419)38:8<1131::aid-anie1131>3.0.co;2-b

  日期：1999.4.19

  Originally discovered as a minor by-product of 6-sulfo-N-acetylsialyl Lewis(x) , the de-N-acetylated form 1 is a superior L-selectin ligand to the N-acetyl form. To substantiate the extraordinary reactivity of 1, it was synthesized for the first time and its binding to L-selectin investigated. Compound 1 and related structures may be high-affinity endogenous ligands for L-selectin that are involved in the interaction of leukocytes with the vascular endothelium.