4-methoxyphenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-galactopyranoside | 41341-54-2

• 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
• 英文名称: 4-methoxyphenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-galactopyranoside
• 英文别名: [(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-(4-methoxyphenyl)sulfanyloxan-2-yl]methyl acetate
• CAS: 41341-54-2
• 化学式: C₂₁H₂₆O₁₀S
• 分子量: 470.497
• InChiKey: BBXRAXYSCXVOAK-IFLJBQAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  32
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  149
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  4-methoxyphenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-galactopyranoside 在 亚碘酰苯 、 氨基甲酸铵 作用下， 以 异丙醇 为溶剂， 反应 3.0h， 以34%的产率得到(S_s)-4-methoxyphenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-galactopyranoside imino-λ⁶-sulfanone
  参考文献：
  名称：

  通过高度化学和立体选择性的NH和O转移至硫糖苷来合成糖基亚砜肟。

  摘要：

  据报道合成了前所未有的和稳定的糖基亚磺酰亚胺。所开发的策略代表了直接由硫糖苷形成高度立体选择性的亚磺酰亚胺的第一个例子。该合成方案已在几种带有不同芳香族和烷基作为S取代基，带有葡萄糖，甘露糖和半乳糖作为糖基单元的β-硫代糖苷上进行了测试。该方法已经扩展到乳糖衍生的硫代糖苷和葡萄糖衍生的次磺酰胺。该过程具有化学选择性和立体选择性，X射线分析证实了结构，并提供了有关硫原子构型的立体化学信息。基于硫化物的空间环境，提出了立体化学结果的模型。

  DOI：

  10.1039/d0ob00647e
• 作为产物：
  描述：

  2,3,4,6-四-O-乙酰基-1-硫代-BETA-D-吡喃半乳糖 、 4-methoxybenzenediazonium tetrafluoroborate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 copper(l) chloride 作用下， 以 乙腈 为溶剂， 反应 0.08h， 以85%的产率得到4-methoxyphenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  在温和条件下铜 (I)-催化 Sandmeyer 型 S-芳基化 1-硫糖与芳基重氮盐

  摘要：

  在温和的反应条件下证明了通过S-芳基化从 1-硫糖制备S-芳基硫糖苷。在氯化铜 (I) 和 DBU 存在下，衍生自葡萄糖、氨基葡萄糖、半乳糖、甘露糖、核糖、麦芽糖和乳糖的多种受保护和未受保护的 1-硫糖与官能化芳基重氮盐发生交叉偶联反应。在 5 分钟内以 55-88% 的收率获得所需的产品。在标准反应条件下可以耐受各种官能团，包括卤素。证明了生物学相关的抗糖尿病药 dapagliflozin S -类似物和熊果苷S -类似物（酪氨酸酶抑制剂）的合成。

  DOI：

  10.1021/acs.joc.2c00930

文献信息

• InBr3-Catalyzed Synthesis of Aryl 1,2-trans-Thio(seleno)glycosides
  作者：Lan Yu、Weihua Xue、Teng Ma、Changwei Li、Haijing Liang、Zhaoyan Wang

  DOI：10.1055/s-0036-1588507

  日期：2017.10

  InBr3 is demonstrated to be an efficient catalyst for reactions of fully acetated aldoses with aryl mercaptans or selenophenol at room temperature, rapidly furnishing the corresponding thioglycosides or selenoglycosides with exclusively 1,2-trans-stereoselectivity. This bromide is an air- and moisture-stable Lewis acid and therefore the reactions can be performed in air atmosphere making the procedure simple to perform.

  InBr3被证明是一种高效的催化剂，可在室温下与芳基巯基或硒酚完全乙酰化的醛糖反应中迅速生成相应的巯基糖或硒基糖，且具有纯粹的1,2-反式选择性。这种溴化物是一种空气和湿气稳定的路易斯酸，因此反应可以在空气氛围中进行，使得操作程序简单。
• Efficient one-pot per-O-acetylation–thioglycosidation of native sugars, 4,6-O-arylidenation and one-pot 4,6-O-benzylidenation–acetylation of S-/O-glycosides catalyzed by Mg(OTf)₂
  作者：Mana Mohan Mukherjee、Nabamita Basu、Aritra Chaudhury、Rina Ghosh

  DOI：10.1039/c6ra23198e

  日期：——

  A sequential one-pot per-O-acetylation–S-/O-glycosidation of native mono and disaccharides under solvent free conditions using 0.5 mole% of Mg(OTf)2 as a non-hygroscopic, recyclable catalyst is reported. Regioselective 4,6-O-arylidenation of glycosides and thioglycosides with benzaldehyde or p-methoxybenzaldehyde dimethyl acetal is catalyzed by 10 mole% of Mg(OTf)2 to produce the corresponding 4,6-O-arylidenated

  据报道，在无溶剂条件下，使用0.5摩尔％的Mg（OTf）2作为非吸湿性，可循环利用的催化剂，对单糖和双糖进行连续一锅过O-乙酰化– S- / O-糖基化反应。糖苷和硫糖苷与苯甲醛或对甲氧基苯甲醛二甲基乙缩醛的区域选择性4,6- O-芳基化反应可通过10摩尔％的Mg（OTf）2催化生成相应的4,6- O-芳基化产物。Mg（OTf）2也可以高产率地介导单糖和二糖基糖苷和硫代糖苷的顺序一锅苯甲基化-乙酰化。
• Synthesis and screening of a small glycomimetic library for inhibitory activity on medically relevant galactoside-specific lectins in assays of increasing biorelevance
  作者：Sabine André、Denis Giguère、Tarun K. Dam、Fred Brewer、Hans-Joachim Gabius、René Roy

  DOI：10.1039/c0nj00277a

  日期：——

  Synthetic introduction of aglyconic substitutions into carbohydrate ligands is an approach toward identifying potent inhibitors of medically relevant lectins. We tested a panel of 27 galactoside/lactoside derivatives harboring varying aglycone moieties together with some O-3/O-3′ functionality toward a biohazardous plant toxin and four human adhesion/growth-regulatory galectins. Differential sensitivity profiles of lectin binding with cases showing activity increase relative to galactose/lactose were revealed by systematic assessments using a solid-phase assay. Quantitative differences between the homologous human proteins could even be detected. Binding of substituted lactosides to galectins-1 and -3 was shown to be enthalpically driven. To determine the potential of substituted glycosides to protect cells from harmful lectin association, binding assays with human tumor cells were performed. Invariably, compounds were identified with increased potency relative to the unsubstituted parent sugars. However, aglyconic substitutions were shown to be able to convey cytotoxicity. This report directs further attention to examining additional 2′- and 3′-substitutions of the galactose core and the potential of ligand presentation in glycoclusters to enhance avidity and selectivity, continuing to use the herein applied strategic combination of a convenient biochemical test system with bioassays.

  在碳水化合物配体中合成引入琼脂取代物，是鉴定医学相关凝集素强效抑制剂的一种方法。我们测试了 27 种半乳糖苷/乳糖苷衍生物，这些衍生物含有不同的琼脂酮分子和一些 O-3/O-3′ 功能，可与一种具有生物危害性的植物毒素和四种人类粘附/生长调节半凝集素结合。通过使用固相分析法进行系统评估，发现了凝集素结合的不同敏感性特征，以及相对于半乳糖/乳糖活性增加的情况。甚至还能检测到同源人类蛋白质之间的数量差异。研究表明，取代的乳糖与半乳糖-1 和半乳糖-3 的结合是由热驱动的。为了确定取代的苷类化合物保护细胞免受有害凝集素结合的潜力，进行了与人类肿瘤细胞的结合试验。与未取代的母糖相比，经鉴定的化合物总是具有更强的效力。不过，琼脂取代物被证明能够传递细胞毒性。本报告引导人们进一步关注研究半乳糖核心的其他 2′-和 3′-取代，以及配体在糖团中的呈递潜力，以提高亲和性和选择性，并继续使用本报告中应用的便捷生化测试系统与生物测定的战略结合。
• Palladium-Catalyzed Cross-Coupling Reaction of Thioglycosides with (Hetero)aryl Halides
  作者：Etienne Brachet、Jean-Daniel Brion、Samir Messaoudi、Mouad Alami

  DOI：10.1002/adsc.201200695

  日期：2013.2.1

  α- and β-thioglycosides serve as effective nucleophiles for Buchwald–Hartwig cross-coupling reactions using functionalized (hetero)aryl halides. The functional group tolerance on the electrophilic partner is typically high, both benzyl and acetate protecting groups on the carbohydrate are tolerated, and anomer selectivities of thioglycosides are high in all cases studied. The efficiency of this general

  α-和β-硫代糖苷可作为使用官能化（杂）芳基卤化物进行布赫瓦尔德-哈特维格交叉偶联反应的有效亲核试剂。在所有研究的案例中，对亲电子试剂的官能团耐受性通常很高，对碳水化合物上的苄基和乙酸酯保护基都可以耐受，并且硫代糖苷的端基选择性很高。合成4-甲基-7-硫代伞形基-β-D-纤维二糖苷（MUS-CB）很好地证明了此通用协议的效率。
• Aryl O- and S-galactosides and lactosides as specific inhibitors of human galectins-1 and -3: Role of electrostatic potential at O-3
  作者：Denis Giguère、Sachiko Sato、Christian St-Pierre、Suzanne Sirois、René Roy

  DOI：10.1016/j.bmcl.2005.12.010

  日期：2006.3

  Phase transfer catalyzed reaction was used for the high yielding synthesis of aryl 1-thio-beta-D-galacto- and lacto-pyranosides carrying a panel of substituents on the phenyl groups. Best galectin-1 inhibitors were simple p-nitrophenyl thiogalactoside 5a for the monosaccharide and o-nitrophenyl thiolactoside 6f or napthylsulfonyl lactoside 8c, both being 20 times better relative to natural ligands. Relative inhibitory properties as low as 2500 and 40 mu M were observed, respectively. The electronic effects of the lactoside aglycons directly influenced the electrostatic potential at O-3, which was associated with the inhibitory potencies against galectin-1. (C) 2006 Elsevier Ltd. All rights reserved.