iso-propyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside | 170428-28-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: iso-propyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside
• 英文别名: (2R,3R,4R,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-propan-2-yloxyoxan-3-ol
• CAS: 170428-28-1
• 化学式: C₃₀H₃₆O₆
• 分子量: 492.612
• InChiKey: CTEMNFRCFHGESM-XZTOTZIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  iso-propyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside 在 乙酸酐 作用下， 以 二甲基亚砜 为溶剂， 生成 isopropyl 3,4,6-tri-O-benzyl-β-D-arabino-hexopyranosid-2-ulose
  参考文献：
  名称：

  Experimental evidence on the hydroxymethyl group conformation in alkyl β-d-mannopyranosides

  摘要：

  A rotational population Study of the hydroxymethyl group of alkyl beta-D-mannopyranosides was performed by means of CD and NMR spectroscopy. Three different benzyl, acetyl, and p-bromobenzoyl series of alkyl beta-D-mannopyranosides with different chiral and nonchiral aglycons were synthesized and analyzed. Different rotational populations were observed for each series by changing the structure of the aglycon. The results showed a clear correlation between the rotational population of the hydroxymethyl group around the C5-C6 bond and the pK(a) of the bonded alcohol (aglycon). The population of the gt rotamer gradually increased as the pK(a) increased while that of the gg rotamer decreased and the population of the tg rotamer remained almost constant. This is explained by the exo-anomeric effect. For chiral alkyl derivatives, the results also showed a close dependence on the absolute configuration of the aglycon. Comparison of rotational population anomers revealed the dependence or the hydroxymethyl group on the anomeric configuration and a greater dependence on the aglycon structure in the beta anomers. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.06.019
• 作为产物：
  描述：

  isopropyl 2-O-(2-(2-nitrophenyl)propyloxycarbonyl)-3,4,6-tri-O-benzyl-β-D-glucopyranoside 以 乙腈 为溶剂， 以91%的产率得到iso-propyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  光不稳定的 2-(2-硝基苯基)-丙氧羰基 (NPPOC) 立体选择性糖基化及其在寡糖连续组装中的应用

  摘要：

  探索了一种光不稳定的保护基团（PPG）2-（2-硝基苯基）-丙氧羰基（NPPOC）在糖基化中的应用，并将其应用于寡糖的连续合成中。NPPOC 显示出强大的邻组参与 (NGP) 效应，以促进 1,2-反式糖苷的高产率构建。值得注意的是，NPPOC可以通过光解有效去除，脱保护条件对典型保护基团友好。快速制备了支链不对称寡甘露糖Man6，并进一步研究了由于NPPPOC光解和糖基化之间的相容性条件而无需中间纯化的寡糖的连续组装。

  DOI：

  10.1021/acs.joc.1c03006

文献信息

• Glycosyl Dithiocarbamates: β-Selective Couplings without Auxiliary Groups
  作者：Panuwat Padungros、Laura Alberch、Alexander Wei

  DOI：10.1021/jo500032k

  日期：2014.3.21

  donors in β-linked oligosaccharide synthesis. We report a mild, one-pot conversion of glycals into β-glycosyl DTCs via DMDO oxidation with subsequent ring opening by DTC salts, which can be generated in situ from secondary amines and CS2. Glycosyl DTCs are readily activated with Cu(I) or Cu(II) triflate at low temperatures and are amenable to reiterative synthesis strategies, as demonstrated by the

  在本文中，我们评估了具有未受保护的 C2 羟基的糖基二硫代氨基甲酸酯 (DTC) 作为 β 连接寡糖合成中的供体。我们报告了通过 DMDO 氧化将糖类一锅温和地转化为 β-糖基 DTC，随后 DTC 盐开环，这可以从仲胺和 CS 2原位生成。糖基 DTCs 在低温下很容易被 Cu(I) 或 Cu(II) 三氟甲磺酸盐激活，并且适合反复合成策略，如三-β-1,6-连接的四糖的有效构建所证明的。尽管不存在预先存在的 C2 辅助基团，但糖基 DTC 偶联具有高度的 β 选择性。我们提供的证据表明，定向效应是由 C2 羟基本身通过顺式稠合双环中间体的假定形成介导的。
• Simple and mild stereoselective O-glycosidation using 1,2-anhydrosugars under neutral conditions
  作者：Devaraj Somasundaram、Kalpattu K. Balasubramanain、Bhagavathy Shanmugasundaram

  DOI：10.1016/j.tetlet.2019.01.049

  日期：2019.3

  of α-d-1,2-anhydrohexapyranoses with phenols proceeded smoothly in ethyl acetate (neutral conditions) in the absence of metal ion catalysts or additives to stereoselectively furnish 1,2-cis-α-aryl glycosides as the major product and 1,2-trans-β-aryl glycosides as the minor product in good yields. Under similar conditions, this ring opening reaction with alcohols afforded exclusively β-alkyl glycosides

  的开环α - d -1,2- anhydrohexapyranoses与酚在没有金属离子的催化剂或添加剂在乙酸乙酯（中性条件）顺利进行立体选择性配料1,2-顺式- α -芳基糖苷作为主要产物和1,2-反式- β -芳基苷作为良好收益次要产物。在相似的条件下，这种与醇的开环反应以优异的产率仅提供β-烷基糖苷。
• Ionic liquids as phase transfer catalysts: Enhancing the biphasic extractive epoxidation reaction for the selective synthesis of β-O-glycosides
  作者：Cintia C. Santiago、Leticia Lafuente、Rodolfo Bravo、Gisela Díaz、Agustín Ponzinibbio

  DOI：10.1016/j.tetlet.2017.08.033

  日期：2017.9

  Ionic liquids promoted the direct epoxidation of glycals acting as PTC. 1,2-anhydrosugars were prepared by the oxidation of glycals under biphasic conditions with dimethydioxirane generated in situ from oxone/acetone and amphiphilic IL’s as catalysts. β-O-glycosides were synthesized in good yields by the nucleophilic ring opening of epoxy carbohydrate derivatives. Also, 3,4,6-benzyl protected carbohydrates

  离子液体促进了充当PTC的糖基的直接环氧化。通过在两相条件下用二氧环乙烷/丙酮和两亲性IL's原位生成的二甲基二环氧乙烷氧化糖类来制备1,2-脱水糖。通过环氧碳水化合物衍生物的亲核开环，可以高收率合成β-O-糖苷。同样，可以通过该方法制备3,4,6-苄基保护的碳水化合物和β-N-糖苷。
• Arylboronic Acid-Mediated Glycosylation of 1,2-Dihydroxyglucoses
  作者：Yoshiji Takemoto、Sanae Izumi、Yusuke Kobayashi

  DOI：10.3987/com-18-s(f)28

  日期：——

  electron-deficient arylboronic acid B1 (X = electron withdrawing group) and 1,2-dihydroxy sugar A, would form borate complex E via coordination of glycosyl acceptor C. Successive intramolecular migration of the coordinated sugar C (RO) to an oxocarbenium ion intermediate (E → F) and ligand exchange of F with diol A would provide the desired glycoside G with 1,2-cis-α-selectivity. Alternatively, using arylboronic

  我们使用一系列芳基硼酸探索了四氢2H-吡喃-2,3-二醇或1,2-二羟基糖与各种醇的直接脱水偶联。在这些催化剂中，2-硼-4-三氟甲基苯甲酸有效地促进了四氢-2H-吡喃-2,3-二醇的缩醛化。二茂铁硼酸对 1,2-二羟基糖的糖基化表现出最好的催化活性。主要产品为 1,2-cis-α-D-吡喃葡萄糖苷。引言 糖基化是合成具有一系列生物活性的寡糖和糖肽的关键步骤。尽管关于糖苷键形成反应的报道很多，但新的高效合成方法仍有待从原子经济性、可持续性、产率和选择性等角度进行探索。在常规的糖基化中，糖基供体带有酰氧基，在合适的布朗斯台德酸或路易斯存在下，需要烷硫基、卤素、2,2,2-三氯-1-亚氨基乙氧基和戊-4-烯氧基在异头位置与糖基受体的游离羟基偶联酸（方案 1a）。活化的糖基供体通常不稳定，需要小心制备和储存。此外，糖基化有时需要超过化学计量量的活化剂或添加剂以及反应混合物的冷却或加热以获得高产率
• Site-Selective Catalysis of Phenyl Thionoformate Transfer as a Tool for Regioselective Deoxygenation of Polyols
  作者：María Sánchez-Roselló、Angela L. A. Puchlopek、Adam J. Morgan、Scott J. Miller

  DOI：10.1021/jo702334z

  日期：2008.3.1

  [Graphics]We report the application of peptide-embedded imidazoles as catalysts for the site-selective delivery of the phenyl thionoformate unit as a prelude to deoxygenation reactions of polyols. Methodology was developed that allows for the synthesis of thiocarboryl derivatives based on a combination of additives that include N-alkylimidazoles and FeCl3 as co-catalysts. The use of this reagent combination leads to increased reaction rates and efficient yields relative to those of simple base-mediated reactions. In terms of controlling regioselectivity during the course of polyol modification, we found that histidine-containing peptides, in combination with FeCl3, could lead to modulation of the product distribution. Through screening of peptides and control of reaction conditions, products could be observed that reflected both the inherent preference of substrates and also reversal of inherent selectivity.