thio [1-thio-β-D-galactopyranose]-(1,1)-S-1-thio-β-D-galactopyranoside | 58524-60-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: thio [1-thio-β-D-galactopyranose]-(1,1)-S-1-thio-β-D-galactopyranoside
• 英文别名: 1,1-dithio-β-digalactopyranoside；1,1'-dithiobis(β-D-galactopyranoside)；1,1'-thio-β-D-digalactopyranoside；bis(1-thio-β-D-galactopyranosyl) 1,1'-disulfide；(2R,3R,4S,5R,6S)-2-(hydroxymethyl)-6-[[(2S,3R,4S,5R,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]disulfanyl]oxane-3,4,5-triol
• CAS: 58524-60-0
• 化学式: C₁₂H₂₂O₁₀S₂
• 分子量: 390.433
• InChiKey: KBTDRQVARMJBHT-ZFDCCPEWSA-N

物化性质

• 沸点：
  734.1±60.0 °C(Predicted)
• 密度：
  1.81±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -3.4
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  231
• 氢给体数：
  8
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  thio [1-thio-β-D-galactopyranose]-(1,1)-S-1-thio-β-D-galactopyranoside 、 D-glucopyranosyl β,β-disulphide 在 sodium hydroxide 、 氘代磷酸 、 六乙基亚磷酸胺 作用下， 以 water-d2 、 氘代乙腈 为溶剂， 生成 D-Glcp-βS(1->1')Sβ-D-Galp
  参考文献：
  名称：

  Phosphine-mediated disulfide metathesis in aqueous media

  摘要：

  通过磷化物介导的二硫化物易位反应，在水性介质中高效合成了动态碳水化合物系统。通过使用1H STD NMR在原位展示了这些动态系统的蛋白质兼容性和结合特性。

  DOI：

  10.1039/c0cc03622f
• 作为产物：
  描述：

  在 氨 、 三乙胺 作用下， 以 甲醇 、 水 为溶剂， 生成 thio [1-thio-β-D-galactopyranose]-(1,1)-S-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  A straightforward synthetic access to symmetrical glycosyl disulfides and biological evaluation thereof

  摘要：

  对称的糖基二硫化物可以通过连续反应方法，在几小时内从全乙酰化前体制备得到，期间无需对任何中间体进行纯化。在最后的硫醇盐氧化成二硫化物步骤中，少量的二苯基二硒化物在空气中能显著加速反应。这个策略对非糖类的对称烷基二硫化物的适用性也进行了研究。对一系列合成的1,1'-二硫化物在两种人类肿瘤细胞系上进行了初步的细胞毒性活性测试，结果表明这些化合物具有显著的活性。

  DOI：

  10.1039/c1ob05619k

文献信息

• Symmetric dithiodigalactoside: strategic combination of binding studies and detection of selectivity between a plant toxin and human lectins
  作者：Sonsoles Martín-Santamaría、Sabine André、Eliza Buzamet、Rémi Caraballo、Gloria Fernández-Cureses、Maria Morando、João P. Ribeiro、Karla Ramírez-Gualito、Beatriz de Pascual-Teresa、F. Javier Cañada、Margarita Menéndez、Olof Ramström、Jesús Jiménez-Barbero、Dolores Solís、Hans-Joachim Gabius

  DOI：10.1039/c0ob01235a

  日期：——

  Thioglycosides offer the advantage over O-glycosides to be resistant to hydrolysis. Based on initial evidence of this recognition ability for glycosyldisulfides by screening dynamic combinatorial libraries, we have now systematically studied dithiodigalactoside on a plant toxin (Viscum album agglutinin) and five human lectins (adhesion/growth-regulatory galectins with medical relevance e.g. in tumor progression and spread). Inhibition assays with surface-presented neoglycoprotein and in solution monitored by saturation transfer difference NMR spectroscopy, flanked by epitope mapping, as well as isothermal titration calorimetry revealed binding properties to VAA (Ka: 1560 ± 20 M−1). They were reflected by the structural model and the affinity on the level of toxin-exposed cells. In comparison, galectins were considerably less reactive, with intrafamily grading down to very minor reactivity for tandem-repeat-type galectins, as quantitated by radioassays for both domains of galectin-4. Model building indicated contact formation to be restricted to only one galactose moiety, in contrast to thiodigalactoside. The tested glycosyldisulfide exhibits selectivity between the plant toxin and the tested human lectins, and also between these proteins. Therefore, glycosyldisulfides have potential as chemical platform for inhibitor design.

  硫糖苷在耐水解方面相对于O-糖苷具有优势。基于初步证据，通过筛选动态组合库，我们对二硫二半乳糖苷在植物毒素（槲寄生凝集素）和五种人类凝集素（与医学相关的粘附/生长调节半乳糖凝集素，例如在肿瘤进展和传播中的作用）进行了系统研究。通过对表面呈现的新型糖蛋白和溶液中的抑制测定，结合饱和转移差异NMR光谱、表位映射，以及等温滴定热量法，揭示了其与槲寄生凝集素（VAA）的结合特性（Ka: 1560 ± 20 M−1）。这些特性通过结构模型以及在暴露于毒素的细胞水平上的亲和力得到了体现。相比之下，半乳糖凝集素的反应性明显较低，在同一家族中，其反应性逐渐降低，特别是对串联重复型半乳糖凝集素的反应性几乎微乎其微，通过对半乳糖凝集素-4的两个结构域进行放射测定来量化。模型构建表明，与二硫二半乳糖苷相比，接触形成仅限于一个半乳糖基团。所测试的糖苷二硫化物在植物毒素和所测试的人类凝集素之间，以及这些蛋白质之间展现出了选择性。因此，糖苷二硫化物在抑制剂设计方面具有作为化学平台的潜力。
• Chemoselective Solution- and Solid-Phase Synthesis of Disulfide-Linked Glycopeptides
  作者：Katreen A. F. Banisalman、Athina Polykandritou、Francis M. Barnieh、Goreti Ribeiro Morais、Robert A. Falconer

  DOI：10.1021/acs.joc.2c01651

  日期：2022.11.4

  glycopeptides. Acetate-protected glycosylsulfenyl hydrazines are shown to be highly reactive with the thiol group of cysteine residues within peptides, both in solution and as part of conventional solid-phase peptide synthesis protocols. The efficiency of this glycosylation methodology with unprotected carbohydrates is also demonstrated, which avoids the need for deprotection steps and further extends its utility

  肽和蛋白质的糖基化是一种广泛采用的策略，用于模拟重要的翻译后修饰或调节肽的物理化学特性以增强其递送。此外，糖基化通过硫原子赋予所得糖缀合物更高的化学和代谢稳定性。在此，我们报告了一种简单且具有化学选择性的程序来制备二硫键连接的糖肽。乙酸盐保护的糖基亚磺酰肼被证明与肽中半胱氨酸残基的硫醇基团具有高度反应性，无论是在溶液中还是作为常规固相肽合成方案的一部分。还证明了这种使用未保护碳水化合物的糖基化方法的效率，它避免了脱保护步骤的需要并进一步扩展了它的实用性，二硫键连接的糖肽以极好的产量产生。鉴于糖基化肽在结构糖生物学、药理学和治疗学中的重要性，
• Synthesis of Carbohydrates with an Anomeric Thiol Moiety for Elaboration into Metabolically Stable Thioglycosides
  作者：Milton J. Kiefel、Robin J. Thomson、Milica Radovanovic、Mark von Itzstein

  DOI：10.1080/07328309908544045

  日期：1999.1.1

  The synthesis of thioglycosides for use as metabolically stable biological probes is an area of continued interest. This paper describes the synthesis of functionalised carbohydrates which contain an anomeric thio group. During the course of this work we have examined the most viable route into compounds such as the specifically functionalised carbohydrates 36 and 37, and have also investigated the usefulness of disulfides as protecting groups for anomeric thiols.
• Disentangling Eumelanin “Black Chromophore”: Visible Absorption Changes As Signatures of Oxidation State- and Aggregation-Dependent Dynamic Interactions in a Model Water-Soluble 5,6-Dihydroxyindole Polymer
  作者：Alessandro Pezzella、Alfonso Iadonisi、Silvia Valerio、Lucia Panzella、Alessandra Napolitano、Matteo Adinolfi、Marco d’Ischia

  DOI：10.1021/ja905162s

  日期：2009.10.28

  A fundamental unsettled issue concerning eumelanins, the functional biopolymers of human skin and hair, is why they are black. The experimental difficulty lies in the virtual insolubility of these pigments, causing marked scattering effects and hindering characterization of the intrinsic absorption properties of the heterogeneous species produced by oxidative polymerization of 5,6-dihydroxyindole (DHI) and related monomer precursors. The synthesis of spectrally robust, water-soluble DHI polymers is therefore an important goal in the prospects of disentangling intrinsic absorption properties of eumelanin components by circumventing scattering effects. Reported herein is the first water-soluble DHI polymer produced by oxidation of ad hoc designed 5,6-dihydroxy-3-indolyl-1-thio-beta-D-galactopyranoside (1). The dark brown polymer exhibited a distinct band at 314 nm and a broad visible absorption, resembling that of natural eumelanins. Main isolable oligomer intermediates including 2,7'- and 2,4'-biindolyls 2 and 3, attest the close resemblance to the mode of coupling of the parent DHI. Sodium borohydride reduction caused decoloration and a marked absorbance decrease in the visible region around 550 nm, but did not affect the UV band at 314 nm. Measurements of absorbance variations with dilution indicated a linear response at 314 rim, but a significant deviation from linearity in the visible region, with the largest decrease around 500 nm. It is argued that eumelanin black color is not only intrinsically defined by the overlap of pi-electron conjugated chromophores within the individual polymer components, as commonly believed, but also by oxidation state- and aggregation-dependent interchromophoric interactions causing perturbations of the heterogeneous ensemble of pi-electron systems and overall spectral broadening.