ethyl 2,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside | 212199-12-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside
• 英文别名: (2S,3R,4S,5S,6R)-2-ethylsulfanyl-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-ol
• CAS: 212199-12-7
• 化学式: C₂₉H₃₄O₅S
• 分子量: 494.652
• InChiKey: BLEKONIUPDUQSX-FOECPVOOSA-N

物化性质

• 沸点：
  645.8±55.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  ethyl 2,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 iodonium(di-γ-collidine) perchlorate 、 4 A molecular sieve 、 sodium methylate 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 22.0h， 生成 2,4,6-tri-O-benzyl-3-O-(p-methoxybenzyl)-α-D-glucopyranosyl-(1-3)-(2,4-di-O-benzyl-α-L-rhamnopyranosyl)-(1-4)-5-O-allyl-1,2,3-tri-O-benzyl-D-ribitol
  参考文献：
  名称：

  合成四个含间隔基的“四糖”，它们代表6B型肺炎链球菌荚膜多糖的四个可能的重复单元。

  摘要：

  3）-α-L-鼠李糖基-（1→4）-5-O-（3-氨丙基磷酸氢盐）-D-核糖醇。磷酸化使用H-膦酸酯方法进行。

  DOI：

  10.1016/s0008-6215(97)10013-1
• 作为产物：
  描述：

  ethyl 3-O-allyl-2,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 Wilkinson's catalyst 水 、 mercury dibromide 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 24.0h， 生成 ethyl 2,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  对应于9型肺炎链球菌荚膜多糖结构的寡糖的合成。

  摘要：

  两种三糖，α-D-Galp-（1-> 3）-beta-D-ManpNAc-（1-> 4）-beta-D-Glcp和alpha-D-Glcp-（1-> 3） -β-D-ManpNAc-（1-> 4）-β-D-Glcp分别对应于肺炎链球菌荚膜多糖9A，L，V和9N型多糖的结构，已被合成为2-氨基乙基糖苷和作为受保护的TMSE糖苷。乙基硫代糖苷用作糖基供体，而NIS / TfOH（对于β键，则在CH（2）Cl（2）中）和DMTST（对于α键，则在Et（2）O中）用作糖基化促进剂。通过叠氮化置换具有β-D-葡萄糖构型的2-O-三氟甲磺酸酯，可以在二糖水平上引入β-ManNAc基序。保护基图案允许连续合成更大的结构。

  DOI：

  10.1016/s0008-6215(02)00263-x

文献信息

• Picoloyl protecting group in synthesis: focus on a highly chemoselective catalytic removal
  作者：Scott A. Geringer、Michael P. Mannino、Mithila D. Bandara、Alexei V. Demchenko

  DOI：10.1039/d0ob00803f

  日期：——

  to be a versatile protecting group in carbohydrate chemistry. It can be used for the purpose of stereocontrolling glycosylations via an H-bond-mediated Aglycone Delivery (HAD) method. It can also be used as a temporary protecting group that can be efficiently introduced and chemoselectively cleaved in the presence of practically all other common protecting groups used in synthesis. Herein, we will describe

  吡啶甲酸酯（Pico）已被证明是碳水化合物化学中的通用保护基。它可以用于通过H键介导的糖苷配基传递（HAD）方法立体控制糖基化的目的。它也可以用作临时保护基团，在合成中使用的所有其他常用保护基团的存在下，可以有效地引入和化学选择性地裂解。在本文中，我们将描述一种使用廉价的铜（II）或铁（III）盐快速，催化和高度化学选择性去除甲基吡啶基的新方法。
• Synthesis of β‐Glucosides with 3‐ <i>O</i> ‐Picoloyl‐Protected Glycosyl Donors in the Presence of Excess Triflic Acid: A Mechanistic Study
  作者：Michael P. Mannino、Alexei V. Demchenko

  DOI：10.1002/chem.201905277

  日期：2020.3.2

  Our previous study showed that picoloylated donors are capable of providing excellent facial stereoselectivity through the H-bond-mediated aglycone delivery (HAD) pathway. Presented herein is a detailed mechanistic study of stereoselective glycosylation with 3-O-picoloylated glucosyl donors. While reactions of glycosyl donors equipped with the 3-O-benzoyl group are typically non-stereoselective because

  我们之前的研究表明，通过氢键介导的糖苷配基传递（HAD）途径，甲基化的供体能够提供出色的面部立体选择性。本文提供了用3-O-吡啶甲基化的葡糖基供体的立体选择性糖基化的详细机理研究。尽管带有3-O-苯甲酰基的糖基供体的反应通常是非立体选择性的，因为这些反应是通过氧杂碳鎓中间体进行的，而3-O-吡啶甲基化的供体能够通过HAD提供增强的，但有些松弛的β-立体选择性。途径。为了改进该反应，我们注意到在NIS和化学计量的TfOH存在下，糖基化具有高度的β-立体选择性。HAD途径极不可能发生，因为在这些反应条件下，皮甲酰氮被质子化。通过低温NMR研究了质子化和糖基化，并观察到了三氟甲磺酸糖基的中间体。本文致力于扩大该反应在各种底物和靶标中的应用范围。
• Synthesis of β‐Glucosides with 3‐ <i>O</i> ‐Picoloyl‐Protected Glycosyl Donors in the Presence of Excess Triflic Acid: Defining the Scope
  作者：Michael P. Mannino、Alexei V. Demchenko

  DOI：10.1002/chem.201905278

  日期：2020.3.2

  Excellent β-stereoselectivity for the glycosylation with glucosyl donors equipped with the 3-O-picoloyl (Pico) group, without the use of participating group, was achieved in the presence of NIS/excess TfOH promoter system. A complete investigation of the scope of this reaction was performed, revealing all important attributes of successful glycosylation. While altering the halogen source was tolerated

  在存在NIS /过量TfOH启动子系统的情况下，在不使用参与基团的情况下，对于配备有3-O-picoloyl（Pico）基团的葡萄糖基供体的糖基化具有出色的β-立体选择性。对该反应范围进行了全面研究，揭示了成功糖基化的所有重要属性。在容忍改变卤素源的同时，三氟甲磺酸根阴离子的取代导致立体选择性的完全丧失。经确定，Pico基团的质子化在该反应中至关重要。还发现质子化吡啶环的稳定性或程度是获得高立体选择性的另一个重要关键因素。发现受体的亲核性与所获得的立体选择性成正比，暗示了类似于SN 2的机制。
• Contribution of Phosphates and Adenine to the Potency of Adenophostins at the IP₃ Receptor: Synthesis of All Possible Bisphosphates of Adenophostin A
  作者：Kana M. Sureshan、Andrew M. Riley、Mark P. Thomas、Stephen C. Tovey、Colin W. Taylor、Barry V. L. Potter

  DOI：10.1021/jm201571p

  日期：2012.2.23

  Although adenophostin A (AdA), the most potent agonist of D-myoinositol 1,4,5-trisphosphate receptors (IP3R), is thought to mimic IP3, the relative roles of the different phosphate groups and the adenosine motif have not been established. We synthesized all three possible bisphosphate analogues of AdA and glucose 3,4-bisphosphate (7, AdA lacking the 2'-AMP). 2'-Dephospho-AdA (6) was prepared via a novel regioselective dephosphorylation strategy. Assessment of the abilities of these bisphosphates to stimulate intracellular Ca2+ release using recombinant rat type 1 IP3R (IP(3)R1) revealed that 6, a mimic of Ins(4,5)P-2, is only 4-fold less potent than IP3, while 7 is some 400-fold weaker and even 3 ''-dephospho-AdA (5) is measurably active, despite missing one of the vicinal bisphosphate groups normally thought to be crucial for IP3-like activity. Compound 6 is the most potent bisphosphate yet discovered with activity at IP3R. Thus, adenosine has a direct role independent of the 2'-phosphate group in contributing toward the potency of adenophostins, the vicinal bisphosphate motif is not essential for activity at the IP3R, as always thought, and it is possible to design potent agonists with just two of the three phosphates. A model with a possible adenine-R504 interaction supports the activity of 5 and 6 and also allows a reappraisal of the unexpected activity previously reported for the AdA regioisomer 2 ''-phospho-3 ''-dephospho-AdA 40.