phenyl 2,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside | 819798-48-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside
• 英文别名: phenyl 2,4,6-O-benzyl-1-thio-β-D-glucopyranoside；Phenyl 2,4,6-tri-O-benzyl-1-thio-beta-D-glucopyranoside；(2R,3S,4S,5R,6S)-3,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-phenylsulfanyloxan-4-ol
• CAS: 819798-48-6
• 化学式: C₃₃H₃₄O₅S
• 分子量: 542.696
• InChiKey: NXYJIFNUJVTKJX-GGJJTXTCSA-N

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 2,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 1-(苯基亚硫酰基)哌啶 、 2,4,6-三叔丁基吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 methyl (3-O-acetyl-2,4,6-tri-O-benzyl-α-D-glucopyranosyl)-(1→2)-3-O-benzyl-4,6-O-benzylidene-α-D-mannopyranoside
  参考文献：
  名称：

  Directing effect by remote electron-withdrawing protecting groups at O-3 or O-4 position of donors in glucosylations and galactosylations

  摘要：

  Glucosylations and galactosylations of various acceptors with donors possessing an electronwithdrawing benzylsulfonyl, benzoyl, or acetyl group at the O-3 or O-4 position were performed. A beta-directing effect by the benzylsulfonyl group at O-3 of the glucosyl donors and by the benzylsulfonyl and acyl groups at O-4 of the glucosyl donors was observed. In contrast, acyl groups at O-3 of the glucosyl donors and acyl groups at O-3 and O-4 of the galactosyl donors exhibited an alpha-directing effect. The alpha-directing effect is partly considered to remote participation of the acyl groups, whereas the beta-directing effect is somewhat attributed to the S(N)2-like reaction of the acceptor with the glycosyl triflate or the contact ion pair, which is stabilized by remote electron-withdrawing groups. Further evidence for the stability of the alpha-glycosyl triflates was determined by a low-temperature NMR study. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.06.014
• 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 methylate 、 potassium hydroxide 作用下， 以 甲醇 为溶剂， 反应 0.5h， 生成 phenyl 2,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Directing effect by remote electron-withdrawing protecting groups at O-3 or O-4 position of donors in glucosylations and galactosylations

  摘要：

  Glucosylations and galactosylations of various acceptors with donors possessing an electronwithdrawing benzylsulfonyl, benzoyl, or acetyl group at the O-3 or O-4 position were performed. A beta-directing effect by the benzylsulfonyl group at O-3 of the glucosyl donors and by the benzylsulfonyl and acyl groups at O-4 of the glucosyl donors was observed. In contrast, acyl groups at O-3 of the glucosyl donors and acyl groups at O-3 and O-4 of the galactosyl donors exhibited an alpha-directing effect. The alpha-directing effect is partly considered to remote participation of the acyl groups, whereas the beta-directing effect is somewhat attributed to the S(N)2-like reaction of the acceptor with the glycosyl triflate or the contact ion pair, which is stabilized by remote electron-withdrawing groups. Further evidence for the stability of the alpha-glycosyl triflates was determined by a low-temperature NMR study. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.06.014

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，
• Organotin-catalyzed regioselective benzylation of carbohydrate trans-diols
  作者：Hengfu Xu、Ying Zhang、Hai Dong、Yuchao Lu、Yuxin Pei、Zhichao Pei

  DOI：10.1016/j.tetlet.2017.08.043

  日期：2017.10

  approach to regioselective benzylation of carbohydrate trans-diols was developed, where 0.1 equiv. of Bu2SnCl2 and 0.1 equiv. of TBABr were used as the catalysts and 2.0 equiv. of BnCl was used as the benzylation reagent. In most cases, similar or better benzylation regioselectivities and isolated yields were obtained by using catalytic amounts of Bu2SnCl2, rather than stoichiometric amounts of organotin

  开发了一种方便的方法，用于碳水化合物反式二醇的区域选择性苄化，其中0.1当量。的Bu 2 SnCl 2和0.1当量 使用TBABr 2的催化剂作为催化剂，当量为2.0当量。将BnCl 2用作苄基化试剂。在大多数情况下，通过使用催化量的Bu 2 SnCl 2而不是所需化学计量的有机锡试剂，可获得相似或更好的苄基化区域选择性和分离的产率。
• Reagent Controlled Stereoselective Assembly of α-(1,3)-Glucans
  作者：Liming Wang、Herman S. Overkleeft、Gijsbert A. van der Marel、Jeroen D. C. Codée

  DOI：10.1002/ejoc.201800894

  日期：2019.3.14

  iodide (TMSI)‐triphenylphosphine oxide (Ph3P=O) for the stereoselective installation of an azidopropanol spacer and triflic acid (TfOH)‐dimethyl formamide (DMF) enabled glycosylations for the coupling reactions with the secondary glucosyl C‐3‐alcohols. An operationally simple in situ activation coupling procedure is introduced and used for the final glycosylation events towards the octasaccharide.

  基于预激活的糖基化已成为寡糖组装中非常强大的工具，并且使用亲核添加剂可以原位生成具有定制反应性的反应性中间体。我们在这里使用一种糖基化策略，该策略基于使用全苄基化亚氨酸酯结构单元来完全立体选择性地构建配备有间隔基的烟曲霉α-1,3-八葡聚糖。我们使用三甲基碘硅烷（TMSI）-三苯基氧化膦（Ph3P=O）来立体选择性安装叠氮丙醇间隔基，并使用三氟甲磺酸（TfOH）-二甲基甲酰胺（DMF）进行糖基化，以与二级葡萄糖基C-3进行偶联反应‐酒精。引入了操作简单的原位激活偶联程序，并将其用于八糖的最终糖基化事件。