6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranose | 88567-49-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranose
• 英文别名: [(2R,3R,4S,5R,6S)-6-hydroxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methyl acetate
• CAS: 88567-49-1
• 化学式: C₂₉H₃₂O₇
• 分子量: 492.569
• InChiKey: RWWBTSOKCOYZSF-RQKPWJHBSA-N

物化性质

• 沸点：
  620.6±55.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranose 在 四溴化碳 、 三苯基膦 作用下， 以 氘代氯仿 为溶剂， 生成 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl bromide
  参考文献：
  名称：

  One-pot α-glycosylation pathway via the generation in situ of α-glycopyranosyl imidates in N,N-dimethylformamide

  摘要：

  Divergent pathways are disclosed in the activation or 2-O-benzyl-1-hydroxy sugars by a reagent combination of CBr4 and Ph3P, all of which afford one-pot alpha-glycosylation methods. When this reagent is used in CH2Cl2, the 1-hydroxy sugar is converted to the alpha-glycosyl bromide in a conventional way and leads to the one-pot a-glycosylation method based on a halide ion-catalytic mechanism. In either DMF or a mixture of DNIF and CHCl3, however, alternative a-glycosyl species are generated. Front the H-1 and C-13 NMR study of the products, as well as the reactions using Vilsmeier reagents [(CH3)(2)N'=CHX]X (X Br and Cl). these were identified as cationic alpha-glycopyranosyl imidates having either Br or Cl counter ion, The cationic alpha-glycosyl imidate (Br), derived specifically in the presence of DMF, is more reactive than the alpha-glycosyl bromide and thus is responsible for the accelerated one-pot alpha-glycosylation. The one-pot alpha-glycosylation methodology performed in DMF was assessed also with different types of acceptor substrates including tertiary alcohols and an anomeric mixture of 1-OH sugars, (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2005.07.020
• 作为产物：
  描述：

  1,6-二-O-乙酰基-2,3,4-三-O-苄基-beta-D-吡喃葡萄糖 在 苄胺 作用下， 反应 3.0h， 生成 6-O-acetyl-2,3,4,-tri-O-benzyl-β-D-glucopyranose 、 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranose
  参考文献：
  名称：

  Enolic Ortho Esters. VI. A New 'Pyranose→Cyclohexane' Transformation via 1,6-Dideoxy-1,1-ethylenedioxy-2,3,4-tri-O-methyl-D-xylo-hex-5-enopyranose

  摘要：

  水解 6-氯-6-脱氧-2,3,4-三-O-甲基-α-D-吡喃葡萄糖苷甲酯 (19b)，并将生成的异构半乙酸酯 (20) 斯韦尔恩氧化，得到 6-氯-6-脱氧-2,3,4-三-O-甲基-D-葡糖酸-1,5-内酯 (21)。 三氟甲磺酸三甲基硅酯的存在下，用 1,2-双（三甲基硅氧基）乙烷处理，得到 6-氯-1,6-二脱氧-1,1-亚乙二氧基-2,3,4-三-O-甲基-D-吡喃葡萄糖（23a）。将 (23a) 转化为相应的 6-碘化合物 (23b)，并用 1,8-二氮杂双环[5.4.0]十一-7-烯处理，可得到烯醇原酯 1,6-二脱氧-1,1-亚乙二氧基-2,3,4-三-O-甲基-D-氧代-己-5-烯吡喃糖 (26)。将 (26) 与甲基碘化镁或四氯化钛反应，分别得到 (1R,6S,7R,8R,9S)-7,8,9-三甲氧基-6-甲基-2,5-二氧杂环[4.3.1]癸烷-1-醇 (34) 或 (2S,3R,4R)-5,5-亚乙二氧基-2,3,4-三甲氧基环己酮 (28)。

  DOI：

  10.1071/ch9960425

文献信息

• An easy α-glycosylation methodology for the synthesis and stereochemistry of mycoplasma α-glycolipid antigens
  作者：Yoshihiro Nishida、Yuko Shingu、Yuan Mengfei、Kazuo Fukuda、Hirofumi Dohi、Sachie Matsuda、Kazuhiro Matsuda

  DOI：10.3762/bjoc.8.70

  日期：——

  Mycoplasma fermentans possesses unique α-glycolipid antigens (GGPL-I and GGPL-III) at the cytoplasm membrane, which carry a phosphocholine group at the sugar primary (6-OH) position. This paper describes a practical synthetic pathway to a GGPL-I homologue (C_16:0) and its diastereomer, in which our one-pot α-glycosylation method was effectively applied. The synthetic GGPL-I isomers were characterized with ¹H NMR spectroscopy to determine the equilibrium among the three conformers (gg, gt, tg) at the acyclic glycerol moiety. The natural GGPL-I isomer was found to prefer gt (54%) and gg (39%) conformers around the lipid tail, while adopting all of the three conformers with equal probability around the sugar position. This property was very close to what we have observed with respect to the conformation of phosphatidylcholine (DPPC), suggesting that the Mycoplasma glycolipids GGPLs may constitute the cytoplasm fluid membrane together with ubiquitous phospholipids, without inducing stereochemical stress.

  Mycoplasma fermentans在细胞膜上具有独特的α-糖脂抗原（GGPL-I和GGPL-III），其中在糖原位（6-OH）位置携带磷胆碱基团。本文描述了一种实用的合成路径，用于合成GGPL-I同分异构体（C_16:0）及其对映异构体，其中我们有效地应用了一锅法α-糖基化方法。合成的GGPL-I同分异构体通过¹H NMR光谱表征，以确定在无环甘油部分的三种构象（gg、gt、tg）之间的平衡。发现天然的GGPL-I同分异构体在脂肪尾部周围更倾向于gt（54%）和gg（39%）构象，而在糖位周围则以相等的概率采用所有三种构象。这种特性与我们观察到的磷脂酰胆碱（DPPC）构象非常接近，表明Mycoplasma的糖脂GGPLs可能与普遍存在的磷脂一起构成细胞质膜，而不会引起立体化学应力。
• Cholesteryl 6-<i>O</i>-acyl-α-glucosides from diverse <i>Helicobacter</i> spp. signal through the C-type lectin receptor Mincle
  作者：Dylan G. M. Smith、Emi Ito、Sho Yamasaki、Spencer J. Williams

  DOI：10.1039/d0ob01776k

  日期：——

  Stereoselective α-glucosylation of cholesterol enabled synthesis of cholesteryl 6-O-acyl-glucosides from diverse Helicobacter spp. and demonstration that they signal through the innate immune receptor Mincle.

  具有立体选择性的胆固醇α-葡萄糖基化使得从不同的幽门螺杆菌（Helicobacter spp.）中合成胆固醇6-O-酰基葡萄糖苷成为可能，并且证明它们通过固有免疫受体Mincle发出信号。
• A Novel Selectfluor-Mediated Regioselective <i>O</i>-Benzyl Ether Acetolysis of Perbenzylated Monosaccharides
  作者：Marlon S. Tambie、Nigel Kevin Jalsa

  DOI：10.1080/07328303.2015.1108423

  日期：2015.11.22

  Selectfluor, a source of the super electrophile F+, has replaced conventional reagents that supply F+ for fluorination due to its attractive physical and chemical properties. This study is the first report of using Selectfluor as a debenzylating reagent. Selectfluor has been found to effect regioselective O- benzyl acetolysis from the per-O-benzylated derivatives of glucose and mannose, which are among the most commonly occurring monosaccharides. For both derivatives, one equivalent of Selectfluor first cleaves the primary benzyl, while a second equivalent subsequently removes the anomeric benzyl. Regioselective removal at higher equivalents proved difficult, with complex mixtures being obtained. The reaction proceeded under mild conditions with good yields and high regioselectivity, resulting in quick access to partially benzylated monosaccharide derivatives. This study provides shortened access to attractive building blocks for oligosaccharide synthesis.
• A highly efficient deprotection of the 2,2,2-trichloroethyl group at the anomeric oxygen of carbohydrates
  作者：Jianbo Zhang、Jie Fu、Wenshuai Si、Xiaohu Wang、Zhongfu Wang、Jie Tang

  DOI：10.1016/j.carres.2011.08.007

  日期：2011.8

  Commercially available zinc dust in the presence of ammonium chloride in acetonitrile at reflux removes the 2,2,2-trichloroethyl (ICE) group at anomeric centers with excellent yields (>95%) in short reaction times. This present method is easily implemented on substrates containing acyl and benzyl groups and large-scale reactions also proceed in high yield. (C) 2011 Elsevier Ltd. All rights reserved.