S-phenyl 2,3-di-O-benzyl-α-D-thiomannopyranoside | 449761-78-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: S-phenyl 2,3-di-O-benzyl-α-D-thiomannopyranoside
• 英文别名: phenyl 2,3-di-O-benzyl-1-thio-α-D-mannopyranoside；phenylthio 2,3-di-O-benzyl-α-D-mannopyranoside；(2R,3R,4S,5S,6R)-2-(hydroxymethyl)-4,5-bis(phenylmethoxy)-6-phenylsulfanyloxan-3-ol
• CAS: 449761-78-8
• 化学式: C₂₆H₂₈O₅S
• 分子量: 452.571
• InChiKey: RCNHWIGTXCJGFF-PUHDZGQXSA-N

物化性质

• 沸点：
  634.1±55.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  S-phenyl 2,3-di-O-benzyl-α-D-thiomannopyranoside 在 吡啶 、 甲醇 、 4-二甲氨基吡啶 、 Stryker's reagent 、 二苯基亚砜 、 水 、 sodium methylate 、 戴斯-马丁氧化剂 、 三氟乙酸 、 三氟乙酸酐 、 2,4,6-三叔丁基嘧啶 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 二氯甲烷-D2 、 苯 为溶剂， 反应 266.17h， 生成 (2R,3S,4S,4aR,6S,8aR)-3,4-bis(benzyloxy)-6-phenyloctahydropyrano[3,2-b]pyran-2-yl trifluoromethanesulfonate
  参考文献：
  名称：

  Influence of O6 in Mannosylations Using Benzylidene Protected Donors: Stereoelectronic or Conformational Effects?

  摘要：

  The stereoselective synthesis of beta-mannosides and the underlying reaction mechanism have been thoroughly studied, and especially the benzylidene-protected mannosides have gained a lot of attention since the corresponding mannosyl triflates often give excellent selectivity. The hypothesis for the enhanced stereoselectivity has been that the benzylidene locks the molecule in a less reactive conformation with the O6 trans to the ring oxygen (O5), which would stabilize the formed alpha-triflate and subsequent give beta-selectivity. In this work, the hypothesis is challenged by using the carbon analogue (C7) of the benzylidene-protected mannosyl donor, which is investigated in terms of diastereoselectivity and reactivity and by low-temperature NMR In terms of diastereoselectivity, the C-7-analogue behaves similarly to the benzylidene-protected donor, but its low-temperature NMR reveals the formation of several reactive intermediate. One of the intermediates was found to be the beta-oxosulfonium ion. The reactivity of the donor was found to be in between that of the "torsional" disarmed and an armed donor.

  DOI：

  10.1021/jo302455d
• 作为产物：
  描述：

  phenyl 2,3-di-O-benzyl-4,6-O-p-methoxybenzylidene-1-thio-α-D-mannopyranoside 在 甲醇 、 camphor-10-sulfonic acid 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 S-phenyl 2,3-di-O-benzyl-α-D-thiomannopyranoside
  参考文献：
  名称：

  Thieme Chemistry Journal Awardees - Where are They Now? Synthesis of the Marine Glycolipid Dioctadecanoyl Discoside

  摘要：

  首次报道了含有肌醇的海洋糖脂二辛酸二硬脂酰基曲霉糖的合成。关键糖基化反应在低温下进行，具有β选择性。可分离的异构体易于推进，从而得到曲霉糖、其全乙酸酯及不自然的β衍生物。

  DOI：

  10.1055/s-0029-1218301

文献信息

• Method of forming glycosidic bonds from thioglycosides using an N,N-dialkylsulfinamide
  申请人：——

  公开号：US20040019198A1

  公开（公告）日：2004-01-29

  A method of forming a glycosidic bond utilizing an activated thioglycoside is disclosed. The thioglycoside is activated by an N,N-dialkylsulfinamide and trifluoromethanesulfonic anhydride. The method allows the facile synthesis of disaccharides, oligosacchraides, and polysaccharides in solution or on a polymer support.

  揭示了一种利用活化硫代糖苷键的方法。该硫代糖苷经N,N-二烷基亚磺酰胺和三氟甲磺酸酐激活。该方法允许在溶液中或在聚合物支撑上轻松合成二糖、寡糖和多糖。
• Glycosylations Directed by the Armed-Disarmed Effect with Acceptors Containing a Single Ester Group
  作者：Thomas H. Schmidt、Robert Madsen

  DOI：10.1002/ejoc.200700347

  日期：2007.8

  A selective glycosylation reaction controlled by the armed-disarmed effect is described by the use of phenyl thioglycosides. The donor thioglycoside is fully protected with benzyl ethers while the acceptor thioglycoside contains benzyl ethers at position 2 and 3 and a strongly electron-withdrawing pentafluorobenzoate ester group at position 6. The coupling can be performed with galactose, glucose,

  通过使用苯基硫糖苷描述了由武装-解除武装效应控制的选择性糖基化反应。供体硫糖苷被苄基醚完全保护，而受体硫糖苷在 2 位和 3 位包含苄基醚，在 6 位包含一个强吸电子的五氟苯甲酸酯基团。偶联可以用半乳糖、葡萄糖、甘露糖和邻苯二甲酰亚胺保护葡萄糖胺以良好的产率提供相应的 1,4-连接的二糖。如果添加另一个受体和更多的促进剂，这些二糖可以作为糖基供体在同一个锅中进行额外的偶联反应。这样，可以在一次操作中实现两次连续的糖基化以提供三糖。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Chemical synthesis of C6-tetrazole ᴅ-mannose building blocks and access to a bioisostere of mannuronic acid 1-phosphate
  作者：Eleni Dimitriou、Gavin J Miller

  DOI：10.3762/bjoc.17.110

  日期：——

  bioisosteric tetrazole. Thioglycosides containing a protected C6-tetrazole are accessed from a C6-nitrile, through dipolar cycloaddition using NaN3 with n-Bu2SnO. We also demonstrate access to orthogonally C4-protected donors, suitable for iterative oligosaccharide synthesis. The development of these building blocks is showcased to access anomeric 3-aminopropyl- and 1-phosphate free sugars containing this non-native

  海藻酸盐是一种生物相容性和工业相关的多糖，其许多重要特性源自其多糖醛酸骨架内的带电荷羧酸根基团。这些羧酸盐的等排替代物的设计和包含将支持提供具有替代物理化学性质的新寡糖/多糖材料。本文介绍了我们合成的甘露糖醛酸结构单元，在羧基 C6 位置用生物等排四唑进行了适当修饰。通过使用 NaN 3和n -Bu 2 的偶极环加成，从 C6-腈获得含有受保护的 C6-四唑的硫糖苷锡。我们还展示了对正交 C4 保护供体的访问，适用于迭代寡糖合成。展示了这些构建块的开发，以获取含有这种非天然基序的异头 3-氨基丙基-和 1-磷酸游离糖。
• Benzylidene Acetal Fragmentation Route to 6-Deoxy Sugars:  Direct Reductive Cleavage in the Presence of Ether Protecting Groups, Permitting the Efficient, Highly Stereocontrolled Synthesis of β-<scp>d</scp>-Rhamnosides from <scp>d</scp>-Mannosyl Glycosyl Donors. Total Synthesis of α-<scp>d</scp>-Gal-(1→3)-α-<scp>d</scp>-Rha-(1→3)- β-<scp>d</scp>-Rha-(1→4)-β-<scp>d</scp>-Glu-OMe, the Repeating Unit of the Antigenic Lipopolysaccharide from <i>Escherichia</i> <i>h</i><i>ermannii</i> ATCC 33650 and 33652
  作者：David Crich、Qingjia Yao

  DOI：10.1021/ja048070j

  日期：2004.7.1

  donors bearing a carboxylated donor on O3 is a highly alpha-selective mannosyl and, after radical fragmentation, alpha-d-rhamnosyl donor. Using this stereoselective glycosylation/radical-fragmentation approach, a concise synthesis of the title tetrasaccharide is realized in which both the beta-d- and alpha-d-rhamnopyranosyl units are obtained in a single step by a double radical fragmentation of the modified

  描述了一种立体控制合成β-d-鼠李吡喃糖苷的方法，其中2，3-O-苄基或相关的4，6-O- [α-（2-（2-碘苯基）乙基硫代羰基）亚苄基]-甘露糖基硫糖苷是首先用于以高收率和立体选择性引入β-d-甘露吡喃糖苷键。糖基化之后，在回流下用三丁基氢化锡在甲苯中的氢化物处理可导致还原性自由基断裂，直接以高收率生成6-脱氧糖。这些在O3上带有羧基供体的供体的变异是高度α-选择性的甘露糖基，而在自由基断裂后为α-d-鼠李糖基供体。使用这种立体选择性糖基化/自由基片段化方法，
• Stereocontrolled Synthesis of <scp>d</scp>- and <scp>l</scp>-β-Rhamnopyranosides with 4-<i>O</i>-6-<i>S</i>-α-Cyanobenzylidene-Protected 6-Thiorhamnopyranosyl Thioglycosides
  作者：David Crich、Linfeng Li

  DOI：10.1021/jo8022439

  日期：2009.1.16

  The synthesis of both enantiomers of a 4-O-6-S-α-cyanobenzylidene-protected 6-thiorhamnopyranosyl thioglycoside is described starting from d-mannnose and l-arabinose derivatives for the d- and l-series, respectively. This donor is effective in the preparation of the corresponding β-glycosides using the 1-benzenesulfinyl piperidine/trifluoromethanesulfonic anhydride protocol. Following desulfurization

  的两种对映体的合成4- ö -6-小号-α-cyanobenzylidene保护-6- thiorhamnopyranosyl硫代糖苷描述从起始d -mannnose和升-arabinose衍生物为d -和升-series分别。该供体可有效地使用 1-苯亚磺酰基哌啶/三氟甲磺酸酐方案制备相应的 β-糖苷。在脱硫并伴随 Raney 镍脱苄基化后，如此形成的 6-硫代-β-甘露糖苷以高产率转化为 β-吡喃鼠李糖苷。