4-methylphenyl 2,3-di-O-acetyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside | 219518-20-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methylphenyl 2,3-di-O-acetyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside
• 英文别名: p-tolyl 2,3-di-O-acetyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside；p-methylphenylthio 4,6-O-benzylidene-2,3-di-O-acetyl-β-D-glucopyranoside；2-Phenyl-6-(p-tolylsulfanyl)-4,4a,6,7,8,8a-hexahydro-2H-pyrano[3,2-d][1,3]dioxine-7,8-diyl diacetate；[(2R,4aR,6S,7R,8S,8aR)-7-acetyloxy-6-(4-methylphenyl)sulfanyl-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] acetate
• CAS: 219518-20-4
• 化学式: C₂₄H₂₆O₇S
• 分子量: 458.532
• InChiKey: BKNQELQNPOSQPY-XOJBGPSCSA-N

物化性质

• 沸点：
  578.2±50.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  106
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4-methylphenyl 2,3-di-O-acetyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside 在 吡啶 、 盐酸 、 sodium azide 、 甲磺酰溴 、 3 Angstroems MS 、 silver trifluoromethanesulfonate 、 sodium cyanoborohydride 、 乙二胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 27.75h， 生成 4-methylphenyl (2,3-di-O-acetyl-4-azido-6-O-benzyl-4-deoxy-β-D-galactopyranosyl)-(1->4)-2-acetamido-6-O-benzyl-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of Lactam and Acetamido Analogues of Sialyl Lewis x Tetrasaccharide and Lewis x Trisaccharide

  摘要：

  Virtually complete regioselective galactosylation of the diol acceptor p-methoxyphenyl 6-O-benzyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranoside (15) with the donors ethyl 3,4-di-O-acetyl-6-O-benzyl-2-deoxy-2-[[(2,2,2-trichloroethoxy)carbonyl]amino]-1-beta-D-galactopyranoside (14), 4-methylphenyl 2,3-di-O-acetyl-4-azido-6-O-benzyl-4-deoxy-1-thio-beta-D-galactopyranoside (30), and 4-methylphenyl 2-O-acetyl-4-azido-6-O-benzyl-4-deoxy-3-O-(methoxyethanoyl)-1-thio-beta-D-galactopyranoside (44) gave the lactose-diamine derivatives 16, 33, and 45, respectively. Fucosylation of the NHAc derivatives of 16 and 33 (17 and 34) with the donor 18 gave, after deprotection and N-acetylation, the 2-NHAc-Le(x) and 4-NKAc-Le(x) trisaccharides 3 and 5, respectively. Removal of the Troc group from the tetrasaccharide intermediate 23, followed by N-acetylation (-->24), gave the NHAc-SLe(x) tetrasaccharide 2. Regioselective sialylation of the partially protected trisaccharide diols 21 and 37 with the sialyl donors 22 and 38 gave, after deprotection and lactamization, the SLe(x)-1'''-->2-lactam 1 and the SLe(x)-1'''-->4'-lactam 4, respectively. The stannylidene acetal of the trisaccharide diol 21 was regioselectively 3-O-alkylated with tert-butyl bromoacetate; reductive removal of the Tree protecting group and addition of methanolic MeONa caused formation of a lactam ring. Compound 40 was thus obtained over four steps in an overall yield of 52%. Deprotection of 40 furnished the Le(x)-3,2-lactam 6 in 74% yield. Fucosylation of the lactose-diamine derivative 46 with donor 18 gave the N-3-Le(x) trisaccharide derivative 47. The azido function of 47 was reduced with H2S, which caused spontaneous closure of a lactam ring. Removal of the protecting groups then gave the Le(x)-3,4-lactam 7. The total yields of 1, 2, 3, 4, 5, and 7 from the monosaccharide starting materials 14, 15, 18, 22, 30, 38, and 44 were 10%, 10%, 22%, 14%, 62%, and 28%, respectively.

  DOI：

  10.1021/jo981204p
• 作为产物：
  描述：

  p-tolyl-2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 sodium methylate 、 对甲苯磺酸 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 42.0h， 生成 4-methylphenyl 2,3-di-O-acetyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis and biological evaluation of a novel MUC1 glycopeptide conjugate vaccine candidate comprising a 4’-deoxy-4’-fluoro-Thomsen–Friedenreich epitope

  摘要：

  选择性抗癌疫苗的开发，提供增强对肿瘤复发和转移的保护，一直是科学界研究的焦点。与肿瘤相关的糖蛋白MUC1代表了癌症免疫疗法的一个成熟靶点，并已被用于构建各种合成疫苗候选物。然而，许多这些疫苗原型存在固有的低免疫原性，并容易在体内迅速降解。为了克服这些缺点，已制备了新型氟化MUC1糖肽-BSA/TTox结合疫苗。用4’F-TF-MUC1-TTox结合物免疫小鼠导致强烈的免疫反应，覆盖了对MUC1的自然耐受性，并产生了选择性的IgG抗体，与MCF-7人类癌细胞上的原生MUC1表位发生交叉反应。

  DOI：

  10.3762/bjoc.11.15

文献信息

• 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。
• [EN] HEPARANASE COMPOUNDS AND METHODS OF USE<br/>[FR] COMPOSÉS HÉPARANASE ET MÉTHODES D'UTILISATION
  申请人：UNIV FLORIDA

  公开号：WO2020219753A1

  公开（公告）日：2020-10-29

  The invention relates to compounds that interact with heparanase, uses in heparanase screening, uses in in vitro and in vivo imaging (e.g., positron emission tomography (PET) and magnetic resonance imaging (MRI)), methods of synthesis, methods of modulating heparanase activity, and methods of treating disease and disorders associated with heparanase. The compounds of the invention are also useful in treating one or more diseases or disorders associated with the function of heparanase.

  这项发明涉及与肝素酶相互作用的化合物，用于肝素酶筛选，用于体外和体内成像（例如正电子发射断层扫描（PET）和磁共振成像（MRI）），合成方法，调节肝素酶活性的方法，以及治疗与肝素酶相关的疾病和疾病的方法。该发明的化合物还可用于治疗与肝素酶功能相关的一个或多个疾病或疾病。
• 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。
• Sulfuric acid immobilized on silica: an efficient promoter for one-pot acetalation–acetylation of sugar derivatives
  作者：Balaram Mukhopadhyay

  DOI：10.1016/j.tetlet.2006.04.118

  日期：2006.6

  Sulfuric acid immobilized on silica gel has been used as an efficient and safe alternative promoter for acetalation and subsequent acetylation of sugar glycosides using stoichiometric reagents without work-up. The synthesis of different types of per-O-acetylated acetals/ketals has been achieved from various types of O- and S-glycosides in excellent yields.

  固定在硅胶上的硫酸已被用作一种高效，安全的替代促进剂，用于使用化学计量试剂进行糖苷的缩醛化和随后的乙酰化，而无需进行后处理。已经从各种类型的O-和S-糖苷以优异的产率实现了不同类型的过-O-乙酰化缩醛/缩酮的合成。
• 2-Bromoethyl glycosides for synthesis of glycoconjugates on solid support
  作者：Ulf Ellervik、Mårten Jacobsson、Jörgen Ohlsson

  DOI：10.1016/j.tet.2005.01.015

  日期：2005.2

  2-Bromoethyl glycosides can easily and in high yields be transformed into sulfones by treatment with a suitable thiol followed by oxidation with mCPBA. The observation that the so formed sulfones were cleaved by treatment with NaOMe/MeOH was used to design a new safety catch linker for synthesis of glycoconjugates on solid support.

  通过用合适的硫醇处理然后用m CPBA氧化，可以容易地并且高产率地将2-溴乙基糖苷转化为砜。通过用NaOMe / MeOH处理裂解如此形成的砜的观察结果被用于设计用于在固体支持物上合成糖缀合物的新的安全捕获接头。