phenyl 2,3,4,6-tetra-O-(4-methoxybenzyl)-1-thio-β-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,4,6-tetra-O-(4-methoxybenzyl)-1-thio-β-D-glucopyranoside
• 英文别名: phenyl 2,3,4,6-tetra-O-(p-methoxybenzyl)-1-thio-β-D-glucopyranoside；phenyl 2,3,4,6-tetra-O-p-methoxybenzyl-1-thio-β-D-glucopyranoside；Mob(-2)[Mob(-3)][Mob(-4)][Mob(-6)]Glc(b)-SPh；(2R,3R,4S,5R,6S)-3,4,5-tris[(4-methoxyphenyl)methoxy]-2-[(4-methoxyphenyl)methoxymethyl]-6-phenylsulfanyloxane
• 化学式: C₄₄H₄₈O₉S
• 分子量: 752.926
• InChiKey: CPIWCFYKTXOJCU-IYFSMEFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  54
• 可旋转键数：
  19
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4,6-tetra-O-(4-methoxybenzyl)-1-thio-β-D-glucopyranoside 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 生成 [(3S,4S)-2,4-dimethyl-3-[(E)-4-tri(propan-2-yl)silyloxy-3-[tri(propan-2-yl)silyloxymethyl]but-1-enyl]-4-[[(2R,3R,4S,5R,6R)-3,4,5-tris[(4-methoxyphenyl)methoxy]-6-[(4-methoxyphenyl)methoxymethyl]oxan-2-yl]oxymethyl]cyclohexen-1-yl]oxy-tri(propan-2-yl)silane
  参考文献：
  名称：

  Toward the Development of a General Chiral Auxiliary. 5. High Diastereofacial Selectivity in Cycloadditions with Trienol Silyl Ethers:  An Application to an Enantioselective Synthesis of (−)-Cassioside

  摘要：

  DOI：

  10.1021/jo961613q
• 作为产物：
  描述：

  (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-(phenylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetate 在 sodium hydride 、 potassium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 phenyl 2,3,4,6-tetra-O-(4-methoxybenzyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Toward the Development of a General Chiral Auxiliary. 5. High Diastereofacial Selectivity in Cycloadditions with Trienol Silyl Ethers:  An Application to an Enantioselective Synthesis of (−)-Cassioside

  摘要：

  DOI：

  10.1021/jo961613q

文献信息

• Remote Electronic Effects by Ether Protecting Groups Fine-Tune Glycosyl Donor Reactivity
  作者：Mads Heuckendorff、Lulu Teressa Poulsen、Henrik H. Jensen

  DOI：10.1021/acs.joc.6b00528

  日期：2016.6.17

  para-substituted benzyl ether protecting groups affect the reactivity of glycosyl donors of the thioglycoside type with the N-iodosuccinimide/triflic acid promoter system. Having electron donating p-methoxy-benzyl ether (PMB) groups increased the reactivity of the donor in comparison to having electron withdrawing p-chloro (PClB) or p-cyanobenzyl ether (PCNB) protecting groups, which decreased the reactivity

  已经确定，对位取代的苄基醚保护基团影响硫代糖苷类型的糖基供体与N-碘琥珀酰亚胺/三氟乙酸促进剂系统的反应性。与具有吸电子对氯基（PClB）或对氰基苄基醚（PCNB）保护基相比，具有给电子的对甲氧基苄基醚（PMB）基增加了供体的反应性，从而降低了糖基给体的反应性相对于母体苄基醚（Bn）保护的糖基供体。这些发现被用于通过调节它们的反应性而在两个苄基化的葡萄糖基供体之间进行第一次武装-解除武装的偶联。另外，本发明描述了高效的钯催化的对氯苄基保护的硫代糖苷的多重氰化和甲氧基化。
• Reengineering Chemical Glycosylation: Direct, Metal-Free Anomeric O-Arylation of Unactivated Carbohydrates
  作者：Nicola Lucchetti、Ryan Gilmour

  DOI：10.1002/chem.201804416

  日期：2018.11.2

  in glycobiology, effective routes to well‐defined carbohydrate probes must be developed. For over a century, glycosylation has been dominated by the formation of the anomeric Csp3−O acetal junction in glycostructures. A dissociative mechanistic spectrum spanning SN1 and SN2 is frequently operational thereby reducing the efficiency. By reengineering this fundamental process, an orthogonal disconnection

  为了维持糖生物学的创新，必须开发出有效的途径来定义明确的碳水化合物探针。一个多世纪以来，糖基化一直以糖结构中异头Csp 3 -O缩醛连接的形成为主导。跨越S N 1和S N的解离机制谱图2的设备经常操作，从而降低了效率。通过对这一基本过程进行重新设计，正交断开使得缩醛可以直接由还原糖形成，而无需进行底物预功能化。稳定的芳基碘鎓盐的使用有助于正式的OH功能化反应。这可使乳糖醇在环境温度下进行温和的，无金属的芳基化反应。除具有生物相关性的二糖和三糖（高达85％）外，还使用多种吡喃糖苷和呋喃糖苷单糖验证了转化效率。使用了增强异头作用的氟化机械探针。可以设想，该策略将证明在基于底物的立体控制下构建复杂的乙缩醛是可扩展的。
• Borinic acid-catalyzed stereo- and site-selective synthesis of β-glycosylceramides
  作者：Kyan A. D’Angelo、Mark S. Taylor

  DOI：10.1039/c7cc01673e

  日期：——

  A method for activation of unprotected ceramides towards stereo- and site-selective glycosylation is described. Two-point binding of a diarylborinic acid catalyst to the ceramide accelerates its reactions with ‘armed’ glycosyl methanesulfonate donors, resulting in the formation of a β-glycosidic linkage at the primary OH group.

  描述了一种将未保护的神经酰胺活化为立体和位点选择性糖基化的方法。二芳基硼酸催化剂与神经酰胺的两点结合可加速其与“武装”糖基甲磺酸酯供体的反应，从而在伯OH基上形成β-糖苷键。
• The Palladium-Catalyzed Glycosylation of Halotropones
  作者：Qi Chen、Ping Lan、Shen Tan、Martin G. Banwell

  DOI：10.1021/acs.orglett.2c04099

  日期：2023.1.20

  A range of mono- and disaccharides, including glucose derivative 10, has been cleanly coupled, in the presence of a Pd catalyst, with various halogenated and structurally distinctive tropones, including “parent” compound 11, to afford the corresponding α- and β-anomeric forms of the tropolone glycosides, e.g., 12 and 13, respectively. Varying the ligand used influences the anomer distribution significantly

  一系列单糖和双糖，包括葡萄糖衍生物10，在 Pd 催化剂存在下，与各种卤化和结构独特的托酮（包括“母体”化合物11 ）干净地偶联，得到相应的 α- 和 β-异头形式的托酚酮糖苷，例如分别为12和13。改变所使用的配体会显着影响端基异构体分布，从而使 α- 或 β- 形式占主导地位。当使用二卤化类肌酸素作为偶联伙伴时，观察到显着的化学选择性和区域选择性。
• Aryl(trifluoroethyl)iodonium Triflimide and Nitrile Solvent Systems: A Combination for the Stereoselective Synthesis of Armed 1,2-<i>trans</i>-β-Glycosides at Noncryogenic Temperatures
  作者：An-Hsiang Adam Chu、Andrei Minciunescu、Clay S. Bennett

  DOI：10.1021/acs.orglett.5b03282

  日期：2015.12.18

  Armed thioglycosides can be activated With aryl(trifluoroethyl)iodonium triflimide in 2:1 CH2Cl2/pivalonitrle or a solvent combination of CH2Cl2, acetonitrile, isobutyronitrile, and pivalonitrile (6:1:1:1) at 0 degrees C for glycosylation reactions that proceed in good yield and:moderate to excellent selectivity (up to 25:1 beta/alpha). Comparison to other common glycosylation promoters reveals that :both the Mixed!, solvent and the iodonium salt promoter are required for stereoselectivity.