1,2,4-orthoacetyl-α-D-glucopyranose | 871918-64-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 1,2,4-orthoacetyl-α-D-glucopyranose
• 英文别名: (1R,3R,5R,6S,7S,8R)-5-(hydroxymethyl)-1-methyl-2,4,9,10-tetraoxatricyclo[4.3.1.03,8]decan-7-ol
• CAS: 871918-64-8
• 化学式: C₈H₁₂O₆
• 分子量: 204.18
• InChiKey: FYAHCZIAHGPNJH-XAZAIFFQSA-N

物化性质

• 沸点：
  375.3±37.0 °C(Predicted)
• 密度：
  1.524±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.5
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2,4-orthoacetyl-α-D-glucopyranose 在 盐酸 、 sodium hydride 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 mineral oil 为溶剂， 反应 1.25h， 生成
  参考文献：
  名称：

  Synthesis of 3,6-O-(o-Xylylene)glucopyranosyl Fluoride, an Axial-Rich Glycosyl Donor of β-Glycosylation

  摘要：

  Despite the reported complete beta-selectivity in glycosylation with 2,4-di-O-benzyl-3,6-O-(o-xylylene)-glucopyranosyl fluoride, its preparation has been inefficient. This paper describes an improved route for the donor, including the formation of the 3,6-bridge on 1,2,4-orthoacetylglucose, the preparation of which was also refined, along with a discovered feature that the 3,6-bridged glucose prefers the furanose form. Although this feature made the synthesis of the desired glucopyranosyl donor difficult, application of thermal glycosylation solved the problem. With a modifiable intermediate, the improved availability of the donor would expand the applications.

  DOI：

  10.1021/jo401395h
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-1,2-O-(S)-(1-ethoxyethylidene)-α-D-glucopyranose 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 对甲苯磺酸 作用下， 以 甲醇 、 1,2-二氯乙烷 为溶剂， 反应 7.0h， 以83%的产率得到1,2,4-orthoacetyl-α-D-glucopyranose
  参考文献：
  名称：

  Synthesis of 3,6-O-(o-Xylylene)glucopyranosyl Fluoride, an Axial-Rich Glycosyl Donor of β-Glycosylation

  摘要：

  Despite the reported complete beta-selectivity in glycosylation with 2,4-di-O-benzyl-3,6-O-(o-xylylene)-glucopyranosyl fluoride, its preparation has been inefficient. This paper describes an improved route for the donor, including the formation of the 3,6-bridge on 1,2,4-orthoacetylglucose, the preparation of which was also refined, along with a discovered feature that the 3,6-bridged glucose prefers the furanose form. Although this feature made the synthesis of the desired glucopyranosyl donor difficult, application of thermal glycosylation solved the problem. With a modifiable intermediate, the improved availability of the donor would expand the applications.

  DOI：

  10.1021/jo401395h

文献信息

• Molecular sieves 5A as an acidic reagent: the discovery and applications
  作者：Noriaki Asakura、Tsukasa Hirokane、Hayato Hoshida、Hidetoshi Yamada

  DOI：10.1016/j.tetlet.2010.11.113

  日期：2011.1

  The first use of molecular sieves (MS) 5A as an acidic reagent is described. We observed the acidic property during a dehydration reaction of 2-methyl-4-phenyl-3-butyn-2-ol. The acidity was sufficient to introduce ethoxyethyl and methoxyisopropyl protecting groups into alcohols. Additionally, the employment of MS 5A improved the synthesis of 1,2,4-orthoacetyl-α-d-glucopyranose at the intramolecular

  描述了分子筛（MS）5A作为酸性试剂的首次使用。我们观察到了2-甲基-4-苯基-3-丁炔-2-醇的脱水反应过程中的酸性。酸度足以将乙氧基乙基和甲氧基异丙基保护基引入醇中。另外，MS 5A的使用改善了分子内原酸酯交换步骤中1,2,4-原乙酰基-α - d-吡喃葡萄糖的合成。在合成的另一步骤中，还应用了MS 4A来证明MS的操作简化了总体操作。
• Indium(III) bromide-mediated β-selective thioglycosylation of 1,2,4-O-orthoacetylglucose derivatives
  作者：Daiki Ikuta、Kazuma Kumagai、Takara Hagimori、Tsukasa Hirokane、Kazutada Ikeuchi、Shinnosuke Wakamori、Hidetoshi Yamada

  DOI：10.1016/j.carres.2022.108609

  日期：2022.9

  e possesses a skew-boat glucopyranose ring whose steric strain is expected to show high reactivity. This study describes the β-selective thioglycosylation of 1,2,4-O-orthoacetyl-α-d-glucose. Indium(III) bromide catalyzes the reaction in trifluoromethylbenzene at ambient temperature in the presence of molecular sieves 4A, resulting in the corresponding thioglycoside product with perfect β-selectivity

  1,2,4 - O-邻乙酰基-α- d-葡萄糖具有斜舟吡喃葡萄糖环，其空间应变预计显示出高反应性。本研究描述了 1,2,4- O-邻乙酰基-α- d-葡萄糖的 β-选择性硫代糖基化。溴化铟 (III) 在分子筛 4A 存在下在环境温度下催化三氟甲基苯中的反应，产生具有完美 β-选择性和高产率的相应硫糖苷产物。所提出的糖基化可能有助于合成具有糖部分的功能分子和天然产物。
• Synthesis of 3,6-<i>O</i>-(<i>o</i>-Xylylene)glucopyranosyl Fluoride, an Axial-Rich Glycosyl Donor of β-Glycosylation
  作者：Noriaki Asakura、Atsushi Motoyama、Takuya Uchino、Kotaro Tanigawa、Hidetoshi Yamada

  DOI：10.1021/jo401395h

  日期：2013.9.20

  Despite the reported complete beta-selectivity in glycosylation with 2,4-di-O-benzyl-3,6-O-(o-xylylene)-glucopyranosyl fluoride, its preparation has been inefficient. This paper describes an improved route for the donor, including the formation of the 3,6-bridge on 1,2,4-orthoacetylglucose, the preparation of which was also refined, along with a discovered feature that the 3,6-bridged glucose prefers the furanose form. Although this feature made the synthesis of the desired glucopyranosyl donor difficult, application of thermal glycosylation solved the problem. With a modifiable intermediate, the improved availability of the donor would expand the applications.