p-tolyl 2,3,4-tri-O-acetyl-1-thio-α-L-rhamnopyranoside | 620951-70-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-tolyl 2,3,4-tri-O-acetyl-1-thio-α-L-rhamnopyranoside
• 英文别名: (2S,3S,4R,5R,6S)-2-Methyl-6-(p-tolylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetate；[(2S,3S,4R,5R,6S)-4,5-diacetyloxy-2-methyl-6-(4-methylphenyl)sulfanyloxan-3-yl] acetate
• CAS: 620951-70-4
• 化学式: C₁₉H₂₄O₇S
• 分子量: 396.461
• InChiKey: IUPHPIKXHZLVMM-RNTHYAPCSA-N

物化性质

• 熔点：
  111-112 °C
• 沸点：
  468.3±45.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  113
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  p-tolyl 2,3,4-tri-O-acetyl-1-thio-α-L-rhamnopyranoside 在 碘 、 silver fluoride 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以80%的产率得到2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl fluoride
  参考文献：
  名称：

  一种简便并使用原位生成的一氟化碘解除武装的糖基氟化物的简便合成（见参考文献。1，38，39，40，41，42，43）

  摘要：

  据报道，使用原位生成的一氟化碘可以轻松，方便地合成解除武装的糖基氟化物。该方法耐受大多数常用的保护基团，并且以非常好的收率仅得到α-异头物产物。

  DOI：

  10.1016/j.tetlet.2012.08.024
• 作为产物：
  描述：

  1,2,3,4-tetra-O-acetyl-L-rhamnopyranose 在 碘 、 六甲基二硅氮烷 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 p-tolyl 2,3,4-tri-O-acetyl-1-thio-α-L-rhamnopyranoside
  参考文献：
  名称：

  Streamlined Synthesis of Per-O-acetylated Sugars, Glycosyl Iodides, or Thioglycosides from Unprotected Reducing Sugars¹

  摘要：

  Solvent-free per-O-acetylation of sugars with stoichiometric acetic anhydride and catalytic iodine proceeds in high yield (90-99%) to give exclusively pyranose products as anomeric mixtures. Without workup, subsequent anomeric substitution employing iodine in the presence of hexamethyldisilane (i.e., TMS-I generated in situ) gives the corresponding glycosyl iodides in 75-95% isolated yield. Alternatively, and without workup, further treatment with dimethyl disulfide or thiol (ethanethiol or thiocresol) gives anomerically pure thioglycosides in more than 75% overall yield.

  DOI：

  10.1021/jo048890e
• 作为试剂：
  描述：

  2,3:4,5-二-O-(1-甲基乙亚基)-D-木糖 在 吡啶 、 N-碘代丁二酰亚胺 、 三氟甲磺酸三甲基硅酯 、 magnesium 、 溶剂黄146 、 p-tolyl 2,3,4-tri-O-acetyl-1-thio-α-L-rhamnopyranoside 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 水 为溶剂， 反应 25.0h， 生成
  参考文献：
  名称：

  Synthesis of α-l-rhamnosyl ceramide and evaluation of its binding with anti-rhamnose antibodies

  摘要：

  An α-L-rhamnosyl ceramide (1, α-L-RhaCer) has been prepared that was recognized by anti-L-rhamnose (anti-Rha) antibodies. During these studies we explored the use of an α-L-rhamnosyl thioglycoside and a trichloroacetimidate as a glycosyl donors. Subsequently, the acceptors desired for glycosylation, 3-O-benzoylazidosphingosine or 3-O-alloxycarbonylsphingosine, were prepared from D-xylose. The thioglycoside donor, 2,3,4-tri-O-acetyl-1-(4-tolyl)thio-α-L-rhamnopyranoside, and the trichloroacetimidate donor, 2,3,4-tri-O-acetyl-1-(2,2,2-trichloroethanimidate)-α-L-rhamnopyranoside, were synthesized in 50% and 78% yield overall, respectively. The synthesis of the glycosylation acceptor employed an addition-fragmentation olefination that was successfully carried out in 53% yield. With the successful synthesis of key intermediates, α-L-RhaCer (1) was prepared without any insurmountable obstacles. Anti-Rha antibodies were prepared in BALB/c mice by immunizing them with rhamnose-ovalbumin (Rha-Ova) with Sigma Adjuvant System (SAS) and the anti-L-Rha antibodies were isolated from the blood sera. Liposomes and EL4 tumor cells were used as model systems to demonstrate the ability of 1 to insert into a lipid bilayer. The interaction of the liposomes or the EL4 cells with α-L-RhaCer (1) and anti-Rha antibodies were investigated by fluorescence microscopy and flow cytometry, respectively, to confirm the ability of glycolipid 1 to be displayed on the tumor cell surface as well as the ability to be recognized by anti-Rha antibodies.

  DOI：

  10.1016/j.bmc.2014.08.002

文献信息

• Synthesis of disaccharide modified berberine derivatives and their anti-diabetic investigation in zebrafish using a fluorescence-based technology
  作者：Lizhen Wang、Haotian Kong、Meng Jin、Xiaobin Li、Rostyslav Stoika、Houwen Lin、Kechun Liu

  DOI：10.1039/d0ob00327a

  日期：——

  (2-NBDG) as a glucose tracker. The results indicated that the modification of berberine with carbohydrate groups could give derivatives with improved anti-diabetic activity, in particular the diglucose modified berberine derivative 1 which could dramatically promote the uptake of 2-NBDG in both zebrafish larvae and their eyes even at very low concentrations. Furthermore, the fluorescence-based anti-diabetic

  小ber碱是天然存在的异喹啉生物碱，由于其多种药理活性，在中国已被用作重要的功能性食品添加剂。小ber碱具有开发出抗2型糖尿病（T2DM）的抗糖尿病药的巨大潜力，因为它可以降低许多动物模型中的血糖水平。但是，小oral碱的低抗糖尿病活性和低的生物利用度（低于5％）大大限制了其实际应用。为了解决这些问题，本文着重于使用一些双糖基团对小ber碱进行结构修饰，因为已证明碳水化合物部分可提高生物利用度并增强药物的受体结合亲和力。使用荧光标记的葡萄糖类似物2-脱氧-2-[（7-硝基-2,1,3-苯并恶二唑-4-基）氨基] -d-葡萄糖在斑马鱼模型中进行了合成化合物的抗糖尿病研究（2-NBDG）作为葡萄糖追踪器。结果表明，用糖基团修饰小ber碱可以得到具有改善的抗糖尿病活性的衍生物，特别是二葡萄糖修饰的小ber碱衍生物1可以显着促进斑马鱼幼虫和眼睛中2-NBDG的摄取，即使在非常低的温度下浓度。此外，
• A Generalized Procedure for the One-Pot Preparation of Glycosyl Azides and Thioglycosides Directly from Unprotected Reducing Sugars under Phase-Transfer Reaction Conditions
  作者：Rishi Kumar、Pallavi Tiwari、Prakas R. Maulik、Anup K. Misra

  DOI：10.1002/ejoc.200500646

  日期：2006.1

  Per-O-acetylated glycosyl azides and thioglycosides were prepared in excellent yield directly from unprotected reducing sugars through in situ generation of per-O-acetylated glycosyl bromides by a generalized one-pot procedure under phase-transfer conditions. Stereoselective products were formed with complete inversion at the anomeric centers of the glycosyl bromides to provide a general high-yielding

  过氧乙酰化糖基叠氮化物和硫代糖苷直接从未保护的还原糖通过通用的一锅法在相转移条件下原位生成过氧乙酰化糖基溴化物，以优异的收率制备。在糖基溴化物的异头中心完全反转形成立体选择性产物，为制备 1,2-反式糖基叠氮化物和硫代糖苷提供了一种通用的高产率方法。（© Wiley-VCH Verlag GmbH & Co. KGaA， 69451 德国魏因海姆，2006）
• Convergent chemical synthesis of the pentasaccharide repeating unit of the O-antigen from E. coli O158
  作者：Ankita Mitra、Balaram Mukhopadhyay

  DOI：10.1039/c6ra13909d

  日期：——

  Synthesis of the pentasaccharide repeating unit of the O-antigen from E. coli O158 through a convergent [3 + 2] strategy is reported. Synthesis of the crucial β-ManNAc moiety was achieved from a β-Glc derivative through inversion of the 2-position by an azide nucleophile in excellent yield. The non-reducing end disaccharide α-D-Gal-(1→3)-β-D-GlcNAc was formed through activation of the thioglycoside

  据报道，通过融合[3 + 2]策略从大肠杆菌O158合成O抗原的五糖重复单元。关键的β-ManNAc部分的合成是由β-Glc衍生物通过叠氮化物亲核试剂将2-位转化而得，且收率很高。非还原性末端二糖α- D- Gal-（1→3）-β- D- GlcNAc是通过硫代糖苷Gal供体的化学选择性活化而形成的。后期TEMPO介导的氧化用于安装所需的糖醛酸部分。在H 2 SO 4-二氧化硅存在下，通过使用NIS活化硫糖苷来完成所需的糖基化反应，具有良好或优异的收率和立体选择性。
• A mild and convenient indium(III) chloride-catalyzed synthesis of thioglycosides
  作者：Saibal Kumar Das、Joyita Roy、Kalusani Anantha Reddy、Chandrasekhar Abbineni

  DOI：10.1016/s0008-6215(03)00355-0

  日期：2003.10

  number of methods available for the preparation of thioglycosides, all of them have one or more disadvantages, especially concerning the time factor and cumbersome workup procedures. Here we report a convenient and high-yielding method for the preparation of thioglycosides.

  糖苷化反应的效率通常涉及高化学产率，以及高/完全的立体选择性和区域选择性。所有这些取决于糖基供体和受体的反应性的相容性。在糖基供体中，由于硫糖苷在许多有机反应中的高度稳定性，因此被广泛使用。尽管有许多方法可用于制备硫糖苷，但它们都具有一个或多个缺点，特别是在时间因素和繁琐的后处理程序方面。在这里，我们报告了一种方便高效的硫糖苷制备方法。
• Synthesis of the Rhamnosyl Trisaccharide Repeating Unit To Mimic the Antigen Determinant of <i>Pseudomonas syringae</i> Lipopolysaccharide
  作者：Chung-Shan Yu、Heng-Yen Wang、Li-Wu Chiang、Kai Pei

  DOI：10.1055/s-2007-965995

  日期：2007.5

  3-benzylidine-protected thio-sugar in a one-pot deprotection manner in a respective ratio of 1:2.5. As do- nors for glycosylation, the thio-sugars of both mono- and disaccha- rides were converted to trichloroacetimido rhamnosides. Through this chemoselective strategy, a trisaccharide was obtained that re- tained an anomeric thio group for coupling with ceramide moieties. Bioassays are in progress.

  三糖 2,3,4-O-三苄基-αL-鼠李糖基-(1→3)-4-O-乙酰基-2-O-苯甲酰基-(1→2)-4-O-乙酰基-3-O-苯甲酰-αL-鼠李糖基-1-(4-甲苯基)硫代-α-L-吡喃鼠李糖苷由硫代糖1-(4-甲苯基)硫代-a,bL-吡喃鼠李糖苷从非还原端到还原端制备。用于构建三糖的两个具有 2-和 3-OH 基团的受体分别以 1:2.5 的比例从 2,3-苄基保护的硫代糖中以一锅脱保护的方式获得。作为糖基化的供体，单糖和双糖的硫代糖都转化为三氯乙亚胺鼠李糖苷。通过这种化学选择性策略，获得了保留异头硫基以与神经酰胺部分偶联的三糖。生物测定正在进行中。