phenyl 2,3,6-tri-O-benzyl-1-thio-α-D-mannopyranoside | 316188-24-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,6-tri-O-benzyl-1-thio-α-D-mannopyranoside
• 英文别名: (2R,3R,4S,5S,6R)-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-phenylsulfanyloxan-3-ol
• CAS: 316188-24-6
• 化学式: C₃₃H₃₄O₅S
• 分子量: 542.696
• InChiKey: JWEXHALGGJAYED-UZGUBXJASA-N

物化性质

• 沸点：
  691.6±55.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  39
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  82.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,6-tri-O-benzyl-1-thio-α-D-mannopyranoside 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 3 Angstroem MS 、 sodium cyanoborohydride 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 48.0h， 生成 benzyl 2-O-benzoyl-6-O-benzyl-3-O-[1,4-dioxo-4-(phenyl 2,3,6-tri-O-benzyl-1-thio-α-D-mannopyranosid-4-O-yl)butyl]-α-D-glucopyranoside
  参考文献：
  名称：

  摘要：

  A series of prearranged glycosides 5, 17, 23, 28, 37 and 41, having a benzyl-protected 1-thiomannosyl donor linked through its positions 2, 3, 4 and 6 via succinate and malonate tethers, respectively, to positions 2, 3, and 6 of a benzyl glucopyranoside acceptor, were prepared by condensation of the respective mannosyl succinates and malonates with suitably protected benzyl glucopyranosides. The prearranged glycosides were intramolecularly coupled under various conditions to give the corresponding, tethered (1 --> 4)-linked disaccharides The yields and anomer ratios of the products of these couplings were interpreted in terms of the thermodynamic stability of the resulting disaccharides. In the case of prearranged glycoside 17, having positions 3 of both the donor and the acceptor linked by a succinate tether, a strong dependence of the diastereoselectivity of the intramolecular glycosylation on the activation procedure was observed. All other cases did not show a significant dependence of the outcome of the anomeric configuration in intramolecular glycosylation on the activation procedure or the solvent.

  DOI：

  10.1002/1522-2675(20001004)83:10<2655::aid-hlca2655>3.0.co;2-u
• 作为产物：
  描述：

  2,3-双-O-(苯基甲基)-4,6-O-[(R)-苯基亚甲基]-1-硫代- a-D--吡喃甘露糖苷苯酯 在 盐酸 、 3 Angstroem MS 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以80%的产率得到phenyl 2,3,6-tri-O-benzyl-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  摘要：

  A series of prearranged glycosides 5, 17, 23, 28, 37 and 41, having a benzyl-protected 1-thiomannosyl donor linked through its positions 2, 3, 4 and 6 via succinate and malonate tethers, respectively, to positions 2, 3, and 6 of a benzyl glucopyranoside acceptor, were prepared by condensation of the respective mannosyl succinates and malonates with suitably protected benzyl glucopyranosides. The prearranged glycosides were intramolecularly coupled under various conditions to give the corresponding, tethered (1 --> 4)-linked disaccharides The yields and anomer ratios of the products of these couplings were interpreted in terms of the thermodynamic stability of the resulting disaccharides. In the case of prearranged glycoside 17, having positions 3 of both the donor and the acceptor linked by a succinate tether, a strong dependence of the diastereoselectivity of the intramolecular glycosylation on the activation procedure was observed. All other cases did not show a significant dependence of the outcome of the anomeric configuration in intramolecular glycosylation on the activation procedure or the solvent.

  DOI：

  10.1002/1522-2675(20001004)83:10<2655::aid-hlca2655>3.0.co;2-u

文献信息

• METHOD OF SYNTHESIZING SUGAR CHAIN
  申请人：MITSUBISHI CHEMICAL CORPORATION

  公开号：EP1640379A1

  公开（公告）日：2006-03-29

  An object of the present invention is to provide a method for efficiently chemically synthesizing biomolecules including a nucleotide (nucleic acid), a peptide (protein), or a sugar chain, as representative examples. The present invention provides a method of solid-phase synthesis of sugar chain(s) for synthesizing multiple types of sugar chains in at least one sugar chain synthesis reaction system comprising multiple types of monosaccharide units, which is characterized in that it comprises changing the temperature in the sugar chain synthesis reaction system depending on the temperature rising rate that has been determined based on a decrease in side reaction(s) in the reaction system as an indicator.

  本发明的目的是提供一种有效地化学合成生物分子的方法，包括核苷酸（核酸）、肽（蛋白质）或糖链等代表性示例。本发明提供了一种固相合成糖链的方法，用于在至少一个糖链合成反应系统中合成多种类型的糖链，其特征在于根据已确定的反应系统中副反应减少的指标，改变糖链合成反应系统中的温度上升速率。
• An improved method for the synthesis of protected glycosyl fluorides from thioglycosides using N,N-diethylaminosulfur trifluoride (DAST)
  作者：Katsuhiko Suzuki、Yukishige Ito、Osamu Kanie

  DOI：10.1016/j.carres.2012.07.003

  日期：2012.10

  examined using N,N-diethylaminosulfur trifluoride (DAST). Although the reaction proceeded without N-bromosuccinimide (NBS), in some cases it was found that the electrophilicity of the Vilsmeier-type electrophilic sulfinium cation species was not sufficient for the activation of certain less-reactive thioglycosides. Here, we report the results of fluorination reactions of a series of monosaccharides using

  使用N，N-二乙基氨基三氟化硫（DAST）检查了硫糖苷直接转化为寡糖合成中常用的糖基氟化物。尽管反应在没有N-溴代琥珀酰亚胺（NBS）的情况下进行，但在某些情况下，发现Vilsmeier型亲电electro阳离子物种的亲电性不足以活化某些反应性较低的硫代糖苷。在这里，我们报告了在不存在NBS的情况下使用DAST进行的一系列单糖氟化反应的结果，并讨论了在存在二甲基（甲硫基）s三氟甲烷磺酸盐（DMTST）的情况下加速反应的过程，从而提高了产品收率。
• Does Neighboring Group Participation by Non-Vicinal Esters Play a Role in Glycosylation Reactions? Effective Probes for the Detection of Bridging Intermediates
  作者：David Crich、Tianshun Hu、Feng Cai

  DOI：10.1021/jo801630m

  日期：2008.11.21

  tert-butyl cation, providing convincing evidence of participation by esters at that position. However, no evidence was found for such a fragmentation of carbonate esters at the 3-O-equatorial, 4-O-axial and -equatorial, and 6-O positions, indicating that neighboring group participation from those sites does not occur under typical glycosylation conditions. Further probes employing a 4-O-(2-carboxy)benzoate

  通过使用叔丁氧羰基酯，探查了在糖吡喃糖基化反应中的相邻基团在各种供体的3-O-轴向和-赤道，4-O-轴向和-赤道以及6-O-位的酯。预期的中间体环状二氧杂环戊烷基阳离子被轴向3-O衍生物打断，导致形成1,3-O-环状碳酸酯，而叔丁基阳离子丢失，这提供了令人信服的证据表明酯参与了那个位置。但是，没有证据表明在3-O-赤道，4-O-轴和-赤道以及6-O位置发生碳酸酯的这种断裂，表明在典型的糖基化作用下不会发生这些基团的邻近基团的参与。条件。使用4-O-（2-羧基）苯甲酸酯和4-O-（4-甲氧基苯甲酸酯）的其他探针，
• Hafnium(IV) tetratriflate in selective reductive carbohydrate benzylidene acetal opening reaction and direct silylation reaction
  作者：Shino Manabe、Yukishige Ito

  DOI：10.1016/j.tetlet.2013.10.011

  日期：2013.12

  regioselective reductive benzylidene ring opening with concurrent silylation reaction. The synthetic conditions were optimized, and the scope and limitations were identified. In addition to glucose and glycosamine derivatives, mannose and galactose were successfully employed as substrates. Various protecting groups such as acetyl, allyl, and benzyl were found to be stable under the reaction conditions. By using

  四三氟甲磺酸（（IV）被证明是有效的催化剂，用于同时进行甲硅烷基化反应的区域选择性还原性亚苄基开环。优化了合成条件，并确定了范围和局限性。除葡萄糖和糖胺衍生物外，甘露糖和半乳糖也被成功用作底物。发现各种保护基如乙酰基，烯丙基和苄基在反应条件下是稳定的。通过使用氘代还原剂，通过S N 1机理推断反应进行。
• Efficient α-Mannosylation of Phenols: The Role of Carbamates as Scavengers for Activated Glycosyl Donors
  作者：Markus Oberthür、Peter Schüler、Sebastian Fischer、Michael Marsch

  DOI：10.1055/s-0032-1316820

  日期：——

  of trichloroacetimidate donors was found to be an efficient method for the α-mannosylation of tyrosine-containing acceptors. Most notably, these conditions are compatible with the commonly used carbamate protecting groups, whereas trichloroacetimidate activation with trimethylsilyl triflate or the use of glycosyl sulfoxides led to diminished yields in the presence of carbamates. In these cases, the competing

  摘要 发现三氯乙酰亚氨酸酯供体的三氟化硼活化是含酪氨酸受体α-甘露糖基化的有效方法。最值得注意的是，这些条件与常用的氨基甲酸酯保护基相容，而在氨基甲酸酯的存在下，三氟甲磺酸三甲基甲硅烷基酯活化三氯乙酰胺酸酯或使用糖基亚砜导致产率降低。在这些情况下，活化的供体与氨基甲酸酯基团的竞争反应被认为是有问题的副反应。利用这种反应性，在非酸性糖基化条件下，通过不同的Boc保护的氨基酸和二肽与糖基亚砜在三氟甲磺酸酐活化下的反应，首次生成了各种糖基氨基甲酸酯。 发现三氯乙酰亚氨酸酯供体的三氟化硼活化是含酪氨酸受体α-甘露糖基化的有效方法。最值得注意的是，这些条件与常用的氨基甲酸酯保护基相容，而在氨基甲酸酯的存在下，三氟甲磺酸三甲基甲硅烷基酯活化三氯乙酰胺酸酯或使用糖基亚砜导致产率降低。在这些情况下，活化的供体与氨基甲酸酯基团的竞争反应被认为是有问题的副反应。利用这种反应性，在非酸性糖基化条件下，通过不同的