methyl 2,3-di-O-acetyl-4,6-di-O-benzylidene-β-D-glucopyranoside | 162426-12-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2,3-di-O-acetyl-4,6-di-O-benzylidene-β-D-glucopyranoside
• 英文别名: methyl 2,3-di-O-acetyl-4,6-O-benzylidene-β-D-glucopyranoside；methyl-[O²,O³-diacetyl-O⁴,O⁶-((R)-benzylidene)-β-D-glucopyranoside]；Methyl-[O²,O³-diacetyl-O⁴,O⁶-((R)-benzyliden)-β-D-glucopyranosid]；[(2R,4aR,6R,7R,8S,8aR)-7-acetyloxy-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] acetate
• CAS: 162426-12-2
• 化学式: C₁₈H₂₂O₈
• 分子量: 366.368
• InChiKey: QOKXXIQSHLLVPF-OOOWVJFSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 2,3-di-O-acetyl-4,6-di-O-benzylidene-β-D-glucopyranoside 在 2,4,6-三甲基吡啶 、 silver trifluoromethanesulfonate 、 三氯化铁 、 sodium cyanoborohydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 吡啶 、 硝基甲烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 336001.25h， 生成 methyl 4-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-2,3,6-tri-O-acetyl-α-D-glucopyranoside
  参考文献：
  名称：

  Hydroxymethyl Rotamer Populations in Disaccharides

  摘要：

  Sixteen methyl glucopyranosyl glucopyranoside disaccharides (methyl beta-D-Glcp(p-Br-Bz)-(1-->alpha)-beta/alpha-D-Glcp) containing beta-glycosidic linkages (1-->2, 1-->3, 1-->4, and 1-->6) were synthesized and analyzed by means of CD and NMR spectroscopy in three different solvents. For each of these four types of disaccharides, a correlation was observed between the hydroxymethyl rotational populations around the C5-C6 bond of the glucopyranosyl residue II with the substituents and the anomeric configuration of the methoxyl group in residue I, as well as with the solvent. Nonbonded interactions, the stereoelectronic exo-anomeric effect, and hydrogen bonding were found to be responsible for the observed rotameric differences. Whereas the rotational populations of the (1-->6)-linked disaccharides are mainly dependent on the exo-anomeric effect, the (1-->2)-bonded disaccharides are strongly dependent on the anomeric configuration at C1, and the (1-->3)- and (1-->4)-linked disaccharides are mainly dependent on the substituents and the solvent. The population of the gt rotamer decreases as nonbonded interactions increase but increases as the exo-anomeric effect becomes greater, as well as in the presence of intramolecular hydrogen bonding to the endocyclic oxygen O5'. Comparison of the hydroxymethyl rotational preferences between our model disaccharides revealed a dependence on the glycosidic linkage type. Thus the population of the gg and gt rotamers decreases/increases from (1-->2)-(beta series), to (1-->6)-, to (1-->2)-(alpha series), to (1-->4)-, and to (1-->3)-bonded disaccharides respectively, while the tg rotamer population remains almost constant (around 20%), except for the (1-->3)- and (1-->4)-linked disaccharides with the intramolecular hydrogen bonding to O5', where this population decreases to 10%.

  DOI：

  10.1021/jo026913o
• 作为产物：
  描述：

  甲基 Β-D-吡喃葡萄糖苷 在 硫酸 作用下， 以 乙腈 为溶剂， 反应 0.92h， 生成 methyl 2,3-di-O-acetyl-4,6-di-O-benzylidene-β-D-glucopyranoside
  参考文献：
  名称：

  固定在二氧化硅上的硫酸：糖衍生物一锅缩醛乙酰化的有效促进剂

  摘要：

  固定在硅胶上的硫酸已被用作一种高效，安全的替代促进剂，用于使用化学计量试剂进行糖苷的缩醛化和随后的乙酰化，而无需进行后处理。已经从各种类型的O-和S-糖苷以优异的产率实现了不同类型的过-O-乙酰化缩醛/缩酮的合成。

  DOI：

  10.1016/j.tetlet.2006.04.118

文献信息

• Efficient one-pot per-O-acetylation–thioglycosidation of native sugars, 4,6-O-arylidenation and one-pot 4,6-O-benzylidenation–acetylation of S-/O-glycosides catalyzed by Mg(OTf)₂
  作者：Mana Mohan Mukherjee、Nabamita Basu、Aritra Chaudhury、Rina Ghosh

  DOI：10.1039/c6ra23198e

  日期：——

  A sequential one-pot per-O-acetylation–S-/O-glycosidation of native mono and disaccharides under solvent free conditions using 0.5 mole% of Mg(OTf)2 as a non-hygroscopic, recyclable catalyst is reported. Regioselective 4,6-O-arylidenation of glycosides and thioglycosides with benzaldehyde or p-methoxybenzaldehyde dimethyl acetal is catalyzed by 10 mole% of Mg(OTf)2 to produce the corresponding 4,6-O-arylidenated

  据报道，在无溶剂条件下，使用0.5摩尔％的Mg（OTf）2作为非吸湿性，可循环利用的催化剂，对单糖和双糖进行连续一锅过O-乙酰化– S- / O-糖基化反应。糖苷和硫糖苷与苯甲醛或对甲氧基苯甲醛二甲基乙缩醛的区域选择性4,6- O-芳基化反应可通过10摩尔％的Mg（OTf）2催化生成相应的4,6- O-芳基化产物。Mg（OTf）2也可以高产率地介导单糖和二糖基糖苷和硫代糖苷的顺序一锅苯甲基化-乙酰化。
• Acylation of carbohydrates over Al2O3: preparation of partially and fully acylated carbohydrate derivatives and acetylated glycosyl chlorides
  作者：Pallavi Tiwari、Anup Kumar Misra

  DOI：10.1016/j.carres.2005.11.035

  日期：2006.2

  protocol does not require the addition of any base or activator. This methodology has been further extended to the selective acylation of carbohydrate diols and the one-pot preparation of acetylated glycosyl chlorides direct from free reducing sugars. The yields obtained in most of the cases are excellent.

  据报道，使用酰氯和固体支持剂Al2O3对碳水化合物衍生物进行选择性和全O酰化。该协议不需要添加任何碱或活化剂。该方法已经进一步扩展到碳水化合物二醇的选择性酰化和直接从游离还原糖直接制备一锅乙酰化糖基氯的方法。在大多数情况下所获得的产量是极好的。
• Efficient Acetylation of Carbohydrates Promoted by Imidazole
  作者：Pallavi Tiwari、Rishi Kumar、Prakas R. Maulik、Anup Kumar Misra

  DOI：10.1002/ejoc.200500555

  日期：2005.10

  An efficient per-O-acetylation of carbohydrate derivatives and unprotected reducing sugars promoted by imidazole is reported. The reaction conditions have been successfully employed to acetylate carbohydrate derivatives containing acid-susceptible functional groups. In most of the cases the yields obtained were excellent. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  据报道，由咪唑促进的碳水化合物衍生物和未受保护的还原糖的有效过-O-乙酰化。该反应条件已成功用于乙酰化含有酸敏感官能团的碳水化合物衍生物。在大多数情况下，获得的产率非常好。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Site‐Selective Acylation of Pyranosides with Immobilized Oligopeptide Catalysts in Flow
  作者：Alexander Seitz、Raffael C. Wende、Peter R. Schreiner

  DOI：10.1002/chem.202203002

  日期：2023.3.28

  We describe the immobilization of oligopeptide catalysts and their use in the site-selective acetylation of different monosaccharides. The catalysts are easy to synthesize, can easily be reused for several reactions, and are able to perform well in first continuous flow experiments.

  我们描述了寡肽催化剂的固定化及其在不同单糖的位点选择性乙酰化中的应用。这些催化剂易于合成，可以很容易地重复用于多个反应，并且能够在首次连续流动实验中表现良好。
• A METHOD FOR THE IDENTIFICATION AND ESTIMATION OF THE 6-HYDROXYL GROUP IN GLUCOSE
  作者：John Walter Hyde Oldham、Jean Kerr Rutherford

  DOI：10.1021/ja01340a056

  日期：1932.1