methyl 2,3,4-tri-O-benzyl-α-L-glucopyranoside | 138794-99-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-benzyl-α-L-glucopyranoside
• 英文别名: methyl 2,3,4-tri-O-benzyl-α-D-glucopyranoside；[(2S,3S,4R,5S,6R)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methanol
• CAS: 138794-99-7
• 化学式: C₂₈H₃₂O₆
• 分子量: 464.558
• InChiKey: MOKYEUQDXDKNDX-AJIIGFCHSA-N

物化性质

• 沸点：
  593.0±50.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.11
• 重原子数：
  34.0
• 可旋转键数：
  11.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  66.38
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  3,5-di-O-benzyl-α-D-ribofuranoside-prop-2-ynyl-1,2-orthobenzoate 、 methyl 2,3,4-tri-O-benzyl-α-L-glucopyranoside 在 gold(III) chloride 、 sodium methylate 作用下， 以 二氯甲烷 、 甲醇 为溶剂， 反应 4.0h， 以80%的产率得到methyl 2,3,4-tri-O-benzyl-6-O-(3,5-di-O-benzyl β-D-ribofuranosyl) α-D-glucopyranoside
  参考文献：
  名称：

  Gold(III)-Catalyzed Glycosidations for 1,2-trans and 1,2-cis Furanosides

  摘要：

  Stereoselective synthesis of furanosides is still a daunting task, unlike the pyranosides, for which several methods exist. Herein, a unified stereoselective strategy for the synthesis of 1,2-trans and 1,2-cis furanosides is revealed for seven out of eight possible isomers of pentoses. The identified protocol gives access to diastereoselective synthesis of α- and β-araf, ribf, lyxf, and α-xylf furanosides. 1,2-trans glycosides were synthesized by the use of propargyl 1,2-orthoesters under gold-catalyzed glycosidation conditions, and subsequently, they are converted into 1,2-cis glycosides through oxidation-reduction as the key functional group transformation. All the reactions are found to be fully diastereoselective, mild, and high yielding.

  DOI：

  10.1021/jo501052y
• 作为产物：
  描述：

  (2R,3S,4R,5R)-2-methoxy-6-methylidene-3,4,5-tris(phenylmethoxy)oxane 在 sodium hydroxide 、 bis(cyclohexanyl)borane 、 双氧水 作用下， 生成 methyl 2,3,4-tri-O-benzyl-β-D-idopyranoside 、 methyl 2,3,4-tri-O-benzyl-α-L-glucopyranoside
  参考文献：
  名称：

  Total syntheses of glucosidase inhibitors, cyclophellitols

  摘要：

  A beta-D-glucosidase inhibitor, cyclophellitol [(1S,2R,3S,4R,5R,6R)-5-hydroxymethyl-7-oxabicyclo[4.1.0]heptane-2,3,4-triol, 1] and its epoxide diastereomer, 1,6-epicyclophellitol (2) have been synthesized by using an intramolecular [3 + 2]-cycloaddition of a nitrile oxide to an alkene as a key step. 2.3,4-Tri-O-benzyl-6,7-dideoxy-D-ido-hept-6-enose (E,Z)-oxime (6) was prepared from L-glucose in 11 steps. Intramolecular cycloaddition of 6 was realized by NaOCl via an intermediary nitrile oxide to afford the isoxazoline, (1S,2R,3S,4S,5R)-3,4,5-tribenzyloxy-2-hydroxy-8-oxa-7-azabicyclo[4.3.0]non-6-enc (7). Hydrogenolysis of 7 followed by a 5-step sequence gave cyclophellitol (1). Compound 2 was synthesized from methyl alpha-D-galactopyranoside by using a conceptually similar route. The glycosidase-inhibiting activities of 2 were examined.

  DOI：

  10.1016/0008-6215(91)89017-a

文献信息

• Phenanthroline‐Catalyzed Stereoretentive Glycosylations
  作者：Fei Yu、Jiayi Li、Paul M. DeMent、Yi‐Jung Tu、H. Bernhard Schlegel、Hien M. Nguyen

  DOI：10.1002/anie.201901346

  日期：2019.5.20

  limitations in synthetic access to well-defined oligosaccharides. Most of the current methods rely on the design of specialized coupling partners to control selectivity during the formation of glycosidic bonds. Reported herein is the use of a commercially available phenanthroline to catalyze stereoretentive glycosylation with glycosyl bromides. The method provides efficient access to α-1,2-cis glycosides. This

  碳水化合物是自然界中许多生物活性分子的基本组成部分。然而，阐明其作用方式的努力往往受到合成获得明确寡糖的限制的阻碍。大多数当前方法依赖于设计专门的偶联配偶体来控制糖苷键形成过程中的选择性。本文报道了使用可商购的菲咯啉来催化与糖基溴的立体保留糖基化。该方法提供了对 α-1,2-cis 糖苷的有效获取。该协议已用于八糖佐剂的大规模合成。密度泛函理论计算以及动力学研究表明，该反应通过双 SN 2 机制进行。
• Influence of Anion-Binding Schreiner’s Thiourea on DMAP Salts: Synergistic Catalysis toward the Stereoselective Dehydrative Glycosylation from 2-Deoxyhemiacetals
  作者：Titli Ghosh、Ananya Mukherji、Pavan K. Kancharla

  DOI：10.1021/acs.joc.0c02473

  日期：2021.1.1

  chemistry between the thiourea and the anions of Bronsted acids. However, we here demonstrate, for the first time, the synergistic effect of the combination of DMAP/HCl/Schreiner’s thiourea in catalyzing dehydrative glycosylation. The variations in the electronic effects of the cationic Bronsted acid part (the protonated DMAP) in the presence of chloride binding Schreiner’s thiourea have been discussed

  胺用作添加剂，以促进或增加硫脲与布朗斯台德酸阴离子之间的主客体化学反应。然而，我们在这里首次证明了DMAP / HCl / Schreiner硫脲的组合在催化脱水糖基化中的协同作用。使用NMR和X射线晶体学技术已经讨论了在存在氯化物结合的Schreiner硫脲的情况下阳离子布朗斯台德酸部分（质子化的DMAP）的电子效应的变化。
• α-Selective Ribofuranosylation of Alcohols with Ribofuranosyl Iodides and Triphenylphosphine Oxide
  作者：Natsuhisa Oka、Rin Kajino、Kaoru Takeuchi、Haruna Nagakawa、Kaori Ando

  DOI：10.1021/jo500632h

  日期：2014.8.15

  Ribofuranosylation of a variety of alcohols with ribofuranosyl iodides in the presence of a base and triphenylphosphine oxide afforded the corresponding α-ribofuranosides with diastereoselectivities ≥ 99:1. This reaction can be carried out under mildly basic conditions and is thus compatible with acid-sensitive functional groups.