ethyl 3,4-O-isopropylidene-1-thio-β-D-galactopyranoside | 172146-95-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3,4-O-isopropylidene-1-thio-β-D-galactopyranoside
• 英文别名: Ethyl 3-O,4-O-isopropylidene-1-thio-beta-D-galactopyranoside；(3aS,4R,6S,7R,7aR)-6-ethylsulfanyl-4-(hydroxymethyl)-2,2-dimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol
• CAS: 172146-95-1
• 化学式: C₁₁H₂₀O₅S
• 分子量: 264.343
• InChiKey: GISQRMABCYZOBZ-SPFKKGSWSA-N

物化性质

• 沸点：
  434.7±45.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  93.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3,4-O-isopropylidene-1-thio-β-D-galactopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 四丁基溴化铵 、 三乙胺 、 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 sodium hydroxide 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 16.0h， 生成 allyl 3-O-(3,4-di-O-benzoyl-6-O-tert-butyldiphenylsilyl-α-D-galactopyranosyl)-2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranoside
  参考文献：
  名称：

  破伤风菌34H合成防冻剂荚膜多糖的四糖重复单元

  摘要：

  Colwellia psychrerythraea 34H是一种嗜冷革兰氏阴性细菌，能够通过产生独特的荚膜多糖（CPS）而在零下温度下存活，该荚膜多糖具有与众所周知的抗冻（glyco）蛋白相似的抗冻特性。合成了CPS的四糖重复单元，它是由交替的氨基糖和糖醛酸部分组成，呈类似糖胺聚糖的形式，带有酰胺连接的苏氨酸（Thr）装饰物，被合成为O-正丙基糖苷。合成面临一些挑战性的特征，例如建立拥挤的[→2）α- D -Gal p（1→]部分以及两个尿嘧啶单元仅用于在其中一个区域选择性插入Thr酰胺，得到的四糖的NMR数据证实了拟南芥（C. psychrerythraeaea）多糖的结构。

  DOI：

  10.1039/c9ob00104b
• 作为产物：
  描述：

  beta-D-半乳糖五乙酸酯 在 甲醇 、 sodium methylate 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 ethyl 3,4-O-isopropylidene-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  基于抗肿瘤疫苗GM3关键中间体二糖化合物 的制备方法

  摘要：

  本发明涉及基于抗肿瘤疫苗GM3关键中间体二糖化合物，属于寡糖合成技术领域，其结构式为：该化合物适用于肿瘤疫苗GM3的合成研究。本发明还提供了该化合物的制备方法，合成路线简洁，操作简单，原料成本低，通用性强，糖基化反应立体选择性好，适用于各类寡糖化合物的合成。

  公开号：

  CN105418700B

文献信息

• Sulfated .alpha.-glycolipid derivatives as cell adhesion inhibitors
  申请人：Bristol-Myers Squibb Company

  公开号：US05663151A1

  公开（公告）日：1997-09-02

  There is provided novel sulfated .alpha.-glycolipid compounds of the formula ##STR1## wherein R is an acyl residue of a fatty acid; R.sup.1 is --(CH.dbd.CH).sub.m --(CH.sub.2).sub.n --CH.sub.3 ; R.sup.2, R.sup.3, R.sup.4 and R.sup.6 are independently at least two --SO.sub.3 H; R.sup.2, R.sup.3, R.sup.4 R.sup.5 and R.sup.6 each are independently hydrogen, unsubstituted or substituted alkanoyl, arylalkyl or arylcarbonyl wherein said substituent is selected from halogen, C.sub.1-4 alkyl, trifluoromethyl, hydroxy and C.sub.1-4 alkoxy; m is an integer of 0 or 1; n is an integer of from 5 to 14, inclusive; or a non-toxic pharmaceutically acceptable salt, solvate or hydrate thereof which are inhibitors of selectin-mediated cellular adhesion and are useful in the treatment or prevention of inflammatory diseases and other pathological conditions in mammals.

  提供了一种新型的磺酸化α-糖脂化合物，其化学式为##STR1##其中R是脂肪酸的酰基残基；R.sup.1是--(CH.dbd.CH).sub.m--(CH.sub.2).sub.n--CH.sub.3；R.sup.2、R.sup.3、R.sup.4和R.sup.6独立地至少有两个--SO.sub.3 H；R.sup.2、R.sup.3、R.sup.4、R.sup.5和R.sup.6各自独立地是氢、未取代或取代的烷酰基、芳基烷基或芳基羰基，其中所述取代基选自卤素、C.sub.1-4烷基、三氟甲基、羟基和C.sub.1-4烷氧基；m是0或1的整数；n是从5到14的整数，包括在内；或其非毒性药学上可接受的盐、溶剂化合物或水合物，它们是选择素介导的细胞粘附的抑制剂，并且在哺乳动物的炎症性疾病和其他病理条件的治疗或预防中是有用的。
• Oligosaccharide recognition by antibodies: Synthesis and evaluation of talose oligosaccharide analogues
  作者：T L Lowary、E Eichler、D R Bundle

  DOI：10.1139/v02-118

  日期：2002.8.1

  A series of monosaccharide (4–6), disaccharide (3,7–12), and trisaccharide (13–15) analogs of the native ligand 2, which fills the binding site of monoclonal antibody Se 155.4, have been synthesized and their bioactivity measured by solid- and solution-phase assays. The syntheses of disaccharide analogs sought to replace galactose by various alkyl groups at the O-2 position of mannose. The activity of one of these O-2 alkyl analogs was 75% of that observed for the trisaccharide and points to only weak net bonding between the solvent exposed galactose residue and the antibody binding site. The synthesis of talose analogs 13 and 14, where the mannose or galactose residues of 2 were replaced by talose produced ligands with activities from one-third to one-half of that seen for the native ligand 2. These activity changes did not exhibit discernable correlations with the ability of talose to disrupt water of solvation.Key words: abequose, 3,6-dideoxy-D-xylo-hexose, talose disaccharide and trisaccharide, antibody oligosaccharide interactions, molecular recognition of carbohydrates, water in antibody complexes, Salmonella LPS, monoclonal antibody Se 155.4, bacterial O-antigen.

  一系列单糖（4-6）、二糖（3、7-12）和三糖（13-15）类似物已经合成，它们是原生配体2的类似物，填充了单克隆抗体Se 155.4的结合位点，并通过固相和溶液相测定了它们的生物活性。二糖类似物的合成旨在将半乳糖替换为甘露糖的O-2位置的各种烷基。其中一种O-2烷基类似物的活性为观察到的三糖活性的75%，表明溶剂暴露的半乳糖残基与抗体结合位点之间只有弱的净键合。通过将原生配体2的甘露糖残基替换为甜菜糖合成了甜菜糖类似物13和14，这些配体的活性为原生配体2的三分之一到一半。这些活性变化与甜菜糖破坏溶剂水的能力之间没有明显的相关性。关键词：阿贝酮，3,6-二去氧-D-木糖-己糖，甜菜糖二糖和三糖，抗体寡糖相互作用，碳水化合物的分子识别，抗体复合物中的水，沙门氏菌LPS，单克隆抗体Se 155.4，细菌O抗原。
• Substituted tetrahydropyrane derivatives, method for producing same, their use as medicine or diagnostic agent, as well as medicine containing same
  申请人：Aventis Pharma Deutschland GmbH

  公开号：US06756489B1

  公开（公告）日：2004-06-29

  Substituted tetrahydropyran derivatives, processes for their preparation, their use as a pharmaceutical or diagnostic, and pharmaceutical comprising them. The invention relates to compounds of the formula I in which the radicals R1, R2, R3, R4, R5 and X have the meaning mentioned in the description, a process for the preparation of the compounds of the formula I on a solid phase, and their use as pharmaceuticals.

  取代的四氢吡喃衍生物，其制备方法，作为药用或诊断用途的使用，以及包含它们的药物。本发明涉及以下式I的化合物 其中基团R1、R2、R3、R4、R5和X的含义如描述中所述，一种在固相上制备上述式I化合物的方法，以及它们作为药物的用途。
• Synthesis of a hexasaccharide corresponding to a porcine zona pellucida fragment that inhibits porcine sperm-oocyte interaction in vitro
  作者：Nynke M. Spijker、Cor A. Keuning、Mariska Hooglugt、Gerrit H. Veeneman、Constant A.A. van Boeckel

  DOI：10.1016/0040-4020(96)00225-6

  日期：1996.4

  The synthesis of hexasaccharide1, [Galβ(1-4)GlcNAc[6OSO3]β(1-3)Galβ(1-4)GlcNAcβ(1-3)Galβ(1-3)GalNAcα-O(CH2)3NH2], which corresponds to a porcine zona pellucida fragment that inhibits porcine sperm-oocyte interaction, is described. Compound1 was obtained from fully protected hexasaccharide2, which was in turn constructed from protected Galβ(1-3)GalNAc disaccharide5, containing an α-linked 3-azidopropyl

  六糖1，[Galβ（1-4）GlcNAc [6OSO 3 ]β（1-3）Galβ（1-4）GlcNAcβ（1-3）Galβ（1-3）GalNAcα-O（CH 2）3的合成描述了NH 2 ]，其对应于抑制猪精子-卵母细胞相互作用的猪透明带片段。化合物1是从完全保护的六糖2中获得的，而六糖2依次由保护的Galβ（1-3）GalNAc二糖5（包含一个与α连接的3-叠氮丙基间隔基）以及乳糖胺衍生物3和4构成。通过将硒代苯基糖苷偶联制备二糖3和46具有含有异头硫代乙基的糖基受体。NIS / TfOH促进了二糖4与5的偶联，得到29，通过选择性除去乙酰丙酰基将其转化为四糖受体30。用3的30进行糖基化，得到保护的六糖2。去除邻苯二甲酰亚胺基，乙酰化，然后选择性去除烯丙基和硫酸化，最后完全脱保护，得到六糖1。
• Is acyl migration to the aglycon avoidable in 2-acyl assisted glycosylation reactions?
  作者：Attila Bérces、Dennis M Whitfield、Tomoo Nukada、Iwona do Santos Z.、Agnes Obuchowska、Jiri J Krepinsky

  DOI：10.1139/v04-059

  日期：2004.7.1

  This report unequivocally separates orthoester formation from acyl transfer for the first time and indicates possible routes to eliminate 2-O-acyl transfer during glycosylation reactions. Experimental evidence is shown that acyl transfer from 2-O-acyl-3,4,6-tri-O-benzyl-D-galactopyranose-derived glycosyl donors decreases in the order formyl > acetyl > pivaloyl. The 2-O-benzoyl derivatives are more variable, in some cases transferring easily, and in others not at all. Density functional theory (DFT) calculations of the structure and energetics of dioxolenium ion and related intermediates suggest that a proton transfer pathway from the nucleophile to O-2 provides an explanation for the observed trends. These DFT calculations of the proton transfer pathway support a mechanism in which a relay molecule is involved. Further DFT calculations used a constraint based on linear combinations of six bond lengths to establish the sequence of bond breaking and bond forming. The calculated anomeric carbon to former carbonyl oxygen bond that breaks during acyl transfer is the longest in the formyl case and shortest in those that exhibit little or no acyl transfer. Rotation about the aromatic to carbonyl Ph—C(=O) bond is different from the alkyl series. Analysis of this proposed TS led to the postulate that 2,6-substitution may hinder rotation even more. Thus, the 2,6-dimethylbenzoyl analogue was synthesized and it does not transfer directly or by rearrangement of its readily formed orthoester. DFT calculations suggested that 2,6-dimethoxybenzoyl should also not transfer easily. Experimentally, this proved to be the case and this new 2-O-acyl protecting group cleaves at 50 °C with a 1 mol/L solution of LiOH in methanol. Thus, a calculated transition state has led to a prototype of a protecting group that solves a major problem in oligosaccharide synthesis.Key words: glycosylation, carbohydrates, quantum chemistry, reaction mechanism, neighboring-group effects.

  这份报告首次明确区分了正酯醚的形成和酰基转移，并指出了在糖基化反应中消除2-O-酰基转移的可能途径。实验证据表明，从2-O-酰基-3,4,6-三-O-苄基-D-半乳糖苷供体中的酰基转移按照甲酰 > 乙酰 > 皮酰的顺序递减。2-O-苯甲酰衍生物更为多变，在某些情况下易于转移，而在其他情况下则不会转移。密度泛函理论（DFT）计算了二氧环离子及相关中间体的结构和能量学，表明从亲核试剂到O-2的质子转移途径解释了观察到的趋势。这些DFT计算的质子转移途径支持了一个涉及继电分子的机制。进一步的DFT计算使用基于六个键长的线性组合的约束来建立键断裂和键形成的顺序。在酰基转移过程中断裂的异常碳到前羰基氧键，在甲酰情况下是最长的，在几乎没有酰基转移的情况下是最短的。芳香环到羰基Ph-C(=O)键的旋转与烷基系列不同。对这个提出的过渡态的分析导致了这样一个假设，即2,6-取代可能会更加阻碍旋转。因此，合成了2,6-二甲基苯甲酰类似物，它不会直接转移，也不会通过其容易形成的正酯醚的重排转移。DFT计算表明，2,6-二甲氧基苯甲酰也不会轻易转移。实验上证明了这一点，这种新的2-O-酰基保护基在甲醇中与1mol/L的氢氧化锂溶液在50°C下裂解。因此，计算出的过渡态导致了一种解决寡糖合成中主要问题的保护基的原型。关键词：糖基化、碳水化合物、量子化学、反应机理、邻基效应。