methyl 4,6-di-O-benzoyl-α-D-glucopyranoside | 80245-06-3

• 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-α-D-glucopyranoside
• 英文别名: [(2R,3S,4R,5R,6S)-3-benzoyloxy-4,5-dihydroxy-6-methoxyoxan-2-yl]methyl benzoate
• CAS: 80245-06-3
• 化学式: C₂₁H₂₂O₈
• 分子量: 402.401
• InChiKey: SIJMJIAXTKVVQU-PLQGUWCTSA-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-α-D-glucopyranoside 在 三氟化硼乙醚 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 生成 methyl 2,3,4-tri-O-benzyl-α-L-fucopyranosyl(1->3)-2-O-acetyl-4,6-di-O-benzoyl-α-D-glucopyranoside
  参考文献：
  名称：

  Saksena, Rina; Deepak, Desh; Khare, Anakshi, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1999, vol. 38, # 7, p. 795 - 799

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl 2,3-di-O-diphenylmetyl-α-D-glucopyranoside 在 palladium on activated charcoal 吡啶 、 氢气 作用下， 以 乙醇 为溶剂， 反应 3.0h， 生成 methyl 4,6-di-O-benzoyl-α-D-glucopyranoside
  参考文献：
  名称：

  Diphenylmethylation of carbohydrate hydroxyl groups by the reaction with diazo(diphenyl)methane

  摘要：

  DOI：

  10.1016/s0008-6215(00)88058-1

文献信息

• 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。
• Mild and Chemoselective Deacetylation Method Using a Catalytic Amount of Acetyl Chloride in Methanol
  作者：B. Kim、Chang-Eun Yeom、So Lee、Young Kim

  DOI：10.1055/s-2005-869838

  日期：——

  Efficient deacetylation of alcohol acetates under mild acidic conditions was accomplished with a catalytic amount of acetyl chloride in methanol. Acetates of various primary, secondary, aromatic and sugar alcohols were successfully deprotected. Highly chemoselective removal of acetyl groups in presence of ­other commonly employed esters was also achieved in excellent yields. The reactivity of this transesterification-mediated deacetyl­ation was found to be directly dependent upon the electronic and steric nature of the acetates.

  在中等酸性条件下，使用催化量的乙酰氯在甲醇中实现了乙酸酯的高效脱乙酰化，成功地对各种伯醇、仲醇、芳香醇和糖醇的乙酸酯进行了脱保护。在其他常用酯存在的情况下，乙酰基的高选择性去除也以优异的产率实现。研究发现，这种通过酯交换介导的脱乙酰化反应的活性直接取决于乙酸酯的电子和立体性质。
• 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
• Diboron-Catalyzed Regio- and 1,2-<i>cis</i>-α-Stereoselective Glycosylation of <i>trans</i>-1,2-Diols
  作者：Shunpei Tomita、Masamichi Tanaka、Michitaka Inoue、Kazuki Inaba、Daisuke Takahashi、Kazunobu Toshima

  DOI：10.1021/acs.joc.0c02093

  日期：2020.12.18

  2-cis-α-stereoselective glycosylations were investigated using 1,2-anhydroglucose donors and trans-1,2-diol sugar acceptors in the presence of a diboron catalyst. The reactions proceeded smoothly to provide the corresponding 1,2-cis-α-glycosides with consistently very high stereoselectivity and were regioselectivity controlled by the protecting groups of the acceptor. The present glycosylation method was applied

  在二硼催化剂存在下，使用1,2-脱水葡萄糖供体和反式-1,2-二醇糖受体研究了区域-和1,2-顺-α-立体选择性糖基化。反应进行顺利，以提供相应的1,2-顺式-α-糖苷，其始终具有非常高的立体选择性，并由受体的保护基团控制了区域选择性。目前的糖基化方法已成功应用于α-1,3-葡聚糖五糖的高效合成。
• A green and convenient method for regioselective mono and multiple benzoylation of diols and polyols
  作者：Xiaoling Zhang、Bo Ren、Jiantao Ge、Zhichao Pei、Hai Dong

  DOI：10.1016/j.tet.2015.12.074

  日期：2016.2

  An efficient method for regioselective benzoylation of diols and polyols was developed. The benzoylation is catalyzed by only 0.2 equiv of benzoate anion in acetonitrile with the addition of a stoichiometric amount of benzoic anhydride under very mild condition, leading to high yields. Compared with all other methods, this method shows particular advantage in regioselective multiple benzoylation of polyols, and in avoiding the use of any metal-based catalysts and any amine bases, which is more environment friendly. (C) 2015 Elsevier Ltd. All rights reserved.