2,6-di-O-Ac-α-D-Glc | 50694-97-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,6-di-O-Ac-α-D-Glc
• 英文别名: [(2R,3S,4S,5R,6S)-5-acetyloxy-3,4-dihydroxy-6-methoxyoxan-2-yl]methyl acetate
• CAS: 50694-97-8
• 化学式: C₁₁H₁₈O₈
• 分子量: 278.259
• InChiKey: JMLKJIAWZMOPNB-NZFPMDFQSA-N

物化性质

• 沸点：
  388.5±42.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.43
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  111.52
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  2,6-di-O-Ac-α-D-Glc 、 4-溴苯甲酰氯 在 吡啶 、 4-二甲氨基吡啶 作用下， 生成 methyl 2,6-di-O-acetyl-3,4-bis(O-(p-bromobenzoyl))-α-D-glucopyranoside
  参考文献：
  名称：

  烷基吡喃葡萄糖苷异构体间CD光谱差异的立体化学研究

  摘要：

  椅子构型的几何形状略有不同，这是在烷基吡喃葡萄糖苷的异构体中观察到的CD光谱差异的根源。该研究使用甲基吡喃葡萄糖苷衍生物作为模型化合物，显示出CD数据，1 H NMR数据和半经验计算之间的优异一致性，并且发现的几何形状令人满意地解释了四色取代的烷基吡喃葡萄糖苷的β-端基异构体观察到的更高振幅。涉及C2上的发色团的2 / 3、2 / 4和2/6的成对相互作用最依赖于端基异构构型，2/4相互作用甚至显示出异头异构体的相反CD符号。另外，发现2/3成对相互作用独立于糖苷配基的结构性质。

  DOI：

  10.1016/s0957-4166(98)00037-8
• 作为产物：
  描述：

  Methyl 3,4-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-1,3-diyl)-α-D-glucopyranoside 在 四丁基氟化铵 作用下， 生成 2,6-di-O-Ac-α-D-Glc
  参考文献：
  名称：

  Acid-catalysed isomerization of the tetraisopropyldisiloxane-1,3-diyl group. Simultaneous protection of two secondary alcoholic functions.

  摘要：

  DOI：

  10.1016/s0040-4039(00)92778-3

文献信息

• Regioselective Deacetylation of Fully Acetylated Mono- and Di-Saccharides With Hydrazine Hydrate
  作者：R Khan、PA Konowicz、L Gardossi、M Matulova、S Degennaro

  DOI：10.1071/ch9960293

  日期：——

  Selective deacetylation reactions of the peracetylated reducing disaccharides (1), (5), (9), (15), β-D- glucopyranose (17) and 2-acetamido-2-deoxy-β-D-glucopyranose (19), with 1.2 equiv. Of hydrazine hydrate in acetonitrile, gave predominantly the corresponding heptaacetates (2), (6), (10), (16), the tetraacetate (18) and the triacetate (20), with the free hydroxy group at C1. Reaction of (1) with 1.2 equiv. of hydrazine hydrate in N,N- dimethylformamide also afforded the heptaacetate (2), but in lower yield. When reactions of (1), (5) and (9) were performed with 2.5 equiv. of hydrazine hydrate, deacetylation also occurred at other positions to afford the corresponding hexaacetates (3), (7), (11) and (12), with hydroxy groups at C 1,2 or C 1,3, and the pentaacetates (4), (8) and (13), with hydroxy groups at C 1,2,3. Maltose octaacetate (9), in addition, yielded the tetraacetate (14) in which the free hydroxy groups were located at C1,2,2',3. Compound (15) on treatment with 2.5 equiv. of hydrazine hydrate afforded an intractable mixture. The reaction of methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside (21) with 2.5 equiv. of hydrazine hydrate gave the 3,4,6-triacetate (22), a mixture of the 2,6- and the 3,6-diacetates (23) and (24), respectively, the 4,6-diacetate (25), and the 6-acetate (26).

  过乙酰化还原二糖 (1)、(5)、(9)、(15)、β-D-吡喃葡萄糖 (17) 和 2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖 (19) 与 1.2 等当量的肼水合物在乙腈中进行选择性脱乙酰化反应，主要得到相应的七乙酸酯 (2)、(6)、(10)、(16)、四乙酸酯 (18)乙腈中的水合肼反应，主要得到相应的七乙酸酯（2）、（6）、（10）、（16）、 四乙酸酯（18）和三乙酸酯（20），其游离羟基位于 C1。将(1)与 1.2 等量的水合肼在 N,N-二甲基甲酰胺中反应，也能得到庚乙酸酯(2)，但产量较低。当用 2.5 等量的水合肼对(1)、(5)和(9)进行反应时，在其他位置也会发生脱乙酰化反应，从而得到相应的六乙酸酯(3)、(7)、(11)和(12)（羟基位于 C 1,2 或 C 1,3）以及五乙酸酯(4)、(8)和(13)（羟基位于 C 1,2,3）。此外，麦芽糖八乙酸酯（9）可生成四乙酸酯（14），其中的游离羟基位于 C1,2,2',3。化合物 (15) 在与 2.5 等量的水合肼处理后，生成了一种难溶于水的混合物。2,3,4,6-O-四乙酰基-α-D-吡喃葡萄糖苷甲酯 (21) 与 2.5 等量的水合肼反应，得到 3,4,6-三乙酸酯 (22)、分别为 2,6- 和 3,6- 二乙酸酯 (23) 和 (24) 的混合物、4,6-二乙酸酯 (25) 和 6- 乙酸酯 (26)。
• Novel methods for the preparation of partially acetylated carbohydrates
  作者：Stephen Hanessian、Masahiro Kagotani

  DOI：10.1016/0008-6215(90)84071-2

  日期：1990.7

  Abstract The selective acetylation of methyl a - d -hexopyranosides in the presence of zinc chloride shows unusual reactivity patterns compared to control experiments. Hydroperoxide ion is a mild and selective deacetylation reagent which does not attack primary acetates.

  摘要在氯化锌存在下，甲基α-d-己吡喃糖苷的选择性乙酰化与对照实验相比，显示出不同寻常的反应模式。氢过氧化物离子是一种温和的，选择性的脱乙酰基试剂，不会侵蚀初级乙酸盐。
• Pyranose benzoates: an additivity relation in the amplitudes of exciton-split CD curves
  作者：Hung Wen Liu、Koji Nakanishi

  DOI：10.1021/ja00369a004

  日期：1982.3
• Directing-protecting groups for carbohydrates. Design, conformational study, synthesis and application to regioselective functionalization
  作者：Nicolas Moitessier、Pablo Englebienne、Yves Chapleur

  DOI：10.1016/j.tet.2005.04.060

  日期：2005.7

  A novel concept of regioselective transformation of secondary hydroxyl groups in carbohydrates is presented. First, the relative reactivity of the free hydroxyl groups of onoprotected D-glucose derivatives was assessed using acetylation as a model reaction. As a result, acylation of these polyols gave it mixture of monosubstituted products in which the 3-O functionalized derivatives predominated. Novel hydrogen bond acceptor protecting groups were next designed to modulate the 4-OH and 3-OH reactivity in the hope to mediate higher regioselective transformations. A molecular modeling study later validated by spectroscopic analysis predicted additional intramolecular hydrogen bonds between the hydroxyl groups and pyridyl-containing protecting groups. Taking advantage of this induced hydrogen bond network. we achieved regioselective acetylation of the hydroxyl group at position 3 without protecting any secondary hydroxyl groups of the carbohydrate moiety. This designed protecting/directing group increased the nucleophilicity and the steric hindrance of position 3. As a result, optimization of the reaction conditions enabled the monoacetylation (not affected by steric hindrance) of 6-O-protected,glucopyranosides at position 3 and selective silylation (affected by steric hindrance) of position 2 in high isolated yields and regioselectivities. This result certainly opens doors to the regioselective open glycosylation of carbohydrates. (c) 2005 Elsevier Ltd. All rights reserved.
• Reagent-Dependent Regioselective Control in Multiple Carbohydrate Esterifications
  作者：Hai Dong、Zhichao Pei、Styrbjörn Byström、Olof Ramström

  DOI：10.1021/jo0620821

  日期：2007.2.1

  Regioselective control in organotin-mediated multiple acylation of carbohydrates is presented. The acylation reagent could be efficiently used to direct the product formation. Reagent-dependent thermodynamic and kinetic control and dynamic assistance mechanisms are suggested, resulting in the efficient preparation of building blocks that normally require many steps with traditional synthesis.