methyl 4,6-di-O-benzoyl-β-D-glucopyranoside | 80245-09-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4,6-di-O-benzoyl-β-D-glucopyranoside
• 英文别名: methyl 4,6-O-dibenzoyl-β-D-glucopyranoside；Methyl-4,6-di-O-benzoyl-β-D-glucopyranosid；[(2R,3S,4R,5R,6R)-3-benzoyloxy-4,5-dihydroxy-6-methoxyoxan-2-yl]methyl benzoate
• CAS: 80245-09-6
• 化学式: C₂₁H₂₂O₈
• 分子量: 402.401
• InChiKey: SIJMJIAXTKVVQU-PDOZGGDVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  112
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 4,6-di-O-benzoyl-β-D-glucopyranoside 、 异丁酸酐 在 (+)-苯并四咪唑 、 N,N-二异丙基乙胺 作用下， 以 氯仿 为溶剂， 反应 12.0h， 以91%的产率得到methyl 4,6-O-dibenzoyl-2-O-isobutyryl-β-D-glucopyranoside
  参考文献：
  名称：

  Catalytic Site-Selective Acylation of Carbohydrates Directed by Cation–n Interaction

  摘要：

  Site-selective functionalization of hydroxyl groups in carbohydrates is one of the long-standing challenges in chemistry. Using a pair of chiral catalysts, we now can differentiate the most prevalent trans-1,2-diols in pyranoses systematically and predictably. Density functional theory (DFT) calculations indicate that the key determining factor for the selectivity is the presence or absence of a cation-n interaction between the cation in the acylated catalyst and an appropriate lone pair in the substrate. DFT calculations also provided a predictive model for site-selectivity and this model is validated by various substrates.

  DOI：

  10.1021/jacs.7b01412
• 作为产物：
  描述：

  methyl 2,3,4,6-tetra-O-benzyl-β-D-glucopyranoside 在 一水合肼 作用下， 以 吡啶 为溶剂， 反应 48.0h， 以30%的产率得到methyl 4,6-di-O-benzoyl-β-D-glucopyranoside
  参考文献：
  名称：

  完全酰化的糖苷和1,2-O-异丙基亚乙基呋喃糖衍生物的区域选择性O-脱酰与水合肼

  摘要：

  摘要在1：4乙酸-吡啶中进行肼解后，在吡啶中，可诱导完全酰化的甲基糖苷和某些其他糖基化合物（23种化合物）的部分O-脱酰作用，从而以较高的收率得到含1种化合物的产物。游离羟基 所得结果表明，在伯和仲O-酰基中，2-O-酰基通常对亲核试剂（肼）最不稳定。另一方面，对1，2-O-异亚丙基戊二醛呋喃糖酰化物（3种化合物）进行水合肼解，以高收率得到相应的在其伯羟基上具有保护基的单酰基衍生物。讨论了可能与肼解的区域选择性有关的因素。

  DOI：

  10.1016/s0008-6215(00)80525-x

文献信息

• Site-Selective and Stereoselective <i>O</i>-Alkylation of Glycosides by Rh(II)-Catalyzed Carbenoid Insertion
  作者：Jicheng Wu、Xiaolei Li、Xiaotian Qi、Xiyan Duan、Weston L. Cracraft、Ilia A. Guzei、Peng Liu、Weiping Tang

  DOI：10.1021/jacs.9b11262

  日期：2019.12.18

  most prevalent trans-1,2-diols in various pyranoses can be systematically and predictably differentiated based on the model derived from DFT calculations. We also demonstrated that the selective O-alkylation method could significantly improve the efficiency and stereoselectivity of glycosylation reactions. The alkyl groups introduced to carbohydrates by OH insertion reaction can serve as functional

  碳水化合物是具有合成挑战性的分子，在所有生命系统中都具有重要的生物学作用。碳水化合物的选择性合成和功能化提供了巨大的机会来提高我们对这一类基本重要分子的生物学功能的理解。然而，碳水化合物中看似相同的羟基的选择性官能化仍然是化学合成中长期存在的挑战。我们在此描述了一种实用且可预测的方法，用于通过 Rh(II) 催化插入金属卡宾中间体对碳水化合物羟基进行位点和立体选择性烷基化。这代表了对碳水化合物进行系统修饰的最温和的烷基化方法之一。密度泛函理论 (DFT) 计算表明，位点选择性是在 Rh(II)-carbenoid 插入步骤中确定的，该步骤更喜欢插入具有相邻轴向取代基的羟基。随后的分子内烯醇质子化决定了意想不到的高立体选择性。基于从 DFT 计算得出的模型，可以系统地和可预测地区分各种吡喃糖中最普遍的反式 1,2-二醇。我们还证明了选择性 O-烷基化方法可以显着提高糖基化反应的效率和立体选择性。通过
• A facile chemoselective deacetylation in the presence of benzoyl and p-bromobenzoyl groups using p-toluenesulfonic acid
  作者：Antonio G González、Ignacio Brouard、Francisco León、Juan I Padrón、Jaime Bermejo

  DOI：10.1016/s0040-4039(01)00406-3

  日期：2001.4

  The acetyl group was chemoselectively cleaved in the presence of p-toluenesulfonic acid (p-TsOH) in CH2Cl2/MeOH without affecting the benzoyl (benzoate and p-bromobenzoate) groups and no transesterification product was observed. The treatment of protected carbohydrates with p-TsOH .H2O at room temperature usually required a longer reaction time than at 40 degreesC. Other types of sulfonic acid such as 10-camphorsulfonic (CSA) led to similar res;lts. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Regioselective O-deacylation of fully acylated glycosides and 1,2-O-isopropylidenealdofuranose derivatives with hydrazine hydrate
  作者：Hoshiharu Ishido、Nobuo Sakairi、Masao Sekiya、Nobuo Nakazaki

  DOI：10.1016/s0008-6215(00)80525-x

  日期：1981.11

  partial O -deacylation of fully acylated methyl glycosides and some other glycosyl compounds (23 compounds) was found to be induced, to give, in good yields, products bearing one free hydroxyl group; the results obtained indicated that, among the primary and secondary O -acyl groups, the 2- O -acyl groups were, in general, the most labile toward the nucleophile (hydrazine). Hydrazinolysis of 1,2- O -

  摘要在1：4乙酸-吡啶中进行肼解后，在吡啶中，可诱导完全酰化的甲基糖苷和某些其他糖基化合物（23种化合物）的部分O-脱酰作用，从而以较高的收率得到含1种化合物的产物。游离羟基 所得结果表明，在伯和仲O-酰基中，2-O-酰基通常对亲核试剂（肼）最不稳定。另一方面，对1，2-O-异亚丙基戊二醛呋喃糖酰化物（3种化合物）进行水合肼解，以高收率得到相应的在其伯羟基上具有保护基的单酰基衍生物。讨论了可能与肼解的区域选择性有关的因素。
• Catalytic Site-Selective Acylation of Carbohydrates Directed by Cation–<i>n</i> Interaction
  作者：Guozhi Xiao、Gabriel A. Cintron-Rosado、Daniel A. Glazier、Bao-min Xi、Can Liu、Peng Liu、Weiping Tang

  DOI：10.1021/jacs.7b01412

  日期：2017.3.29

  Site-selective functionalization of hydroxyl groups in carbohydrates is one of the long-standing challenges in chemistry. Using a pair of chiral catalysts, we now can differentiate the most prevalent trans-1,2-diols in pyranoses systematically and predictably. Density functional theory (DFT) calculations indicate that the key determining factor for the selectivity is the presence or absence of a cation-n interaction between the cation in the acylated catalyst and an appropriate lone pair in the substrate. DFT calculations also provided a predictive model for site-selectivity and this model is validated by various substrates.