isopropyl 3,4,6-tri-O-benzyl-α-D-glucopyranoside | 170428-27-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: isopropyl 3,4,6-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: isopropyl 3,4,6-tri-O-benzyl-D-glucopyranoside；(2S,3R,4R,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-propan-2-yloxyoxan-3-ol
• CAS: 170428-27-0
• 化学式: C₃₀H₃₆O₆
• 分子量: 492.612
• InChiKey: CTEMNFRCFHGESM-WYQCABFXSA-N

物化性质

• 沸点：
  618.0±55.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

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：

  isopropyl 3,4,6-tri-O-benzyl-α-D-glucopyranoside 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 18.0h， 以77%的产率得到isopropyl α-D-glucopyranoside
  参考文献：
  名称：

  Site-Selective Catalysis of Phenyl Thionoformate Transfer as a Tool for Regioselective Deoxygenation of Polyols

  摘要：

  [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.

  DOI：

  10.1021/jo702334z
• 作为产物：
  描述：

  2-methoxy-2-(S)-phenyl-(3,4,6-tri-O-benzyl-1,2-dideoxy-β-D-glucopyranoso)[1,2-e]-1,4-oxathiane (R)-S-oxide 、 异丙醇 在 1,3,5-三甲氧基苯 、 三氟甲磺酸酐 、 N,N-二异丙基乙胺 、 甲醇 、 三氟化硼乙醚 作用下， 以 1,2-二氯乙烷 、 二氯甲烷 为溶剂， 反应 0.5h， 以77%的产率得到isopropyl 3,4,6-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  使用oxathiane糖基供体的立体选择性糖基化。

  摘要：

  双环糖基供体被活化为芳基ulf离子，并用于合成具有高立体选择性的α-糖苷。

  DOI：

  10.1039/b913308a

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。
• Stereoselective glycosylations using oxathiane spiroketal glycosyl donors
  作者：Martin A. Fascione、Nicola J. Webb、Colin A. Kilner、Stuart L. Warriner、W. Bruce Turnbull

  DOI：10.1016/j.carres.2011.07.020

  日期：2012.2

  (TMP)- and 2,4-dimethoxyphenyl (DMP)-oxathiane spiroketal sulfonium ions is discussed, and their α-stereoselectivity in glycosylation reactions is compared to the analogous TMP- and DMP-sulfonium ions derived from an oxathiane glycosyl donor bearing a methyl ketal group. The results show that the stereoselectivity of the oxathiane glycosyl donors is dependent on the structure of the ketal group and

  已经合成了新型的氧杂蒽酮螺环供体，并通过使用1,3,5-三甲氧基苯和1,3-二甲氧基苯的umpolung S-芳基化策略进行活化。讨论了所得的2,4,6-三甲氧基苯基（TMP）-和2,4-二甲氧基苯基（DMP）-氧杂蒽基螺酮tal离子的比较反应性，并将它们在糖基化反应中的α-立体选择性与类似的TMP-衍生自带有甲基缩酮基的氧杂蒽基糖基供体的DMP-离子。结果表明，氧杂蒽基糖基供体的立体选择性取决于缩酮基的结构，并且可以通过改变sulf离子上的取代基来调节反应性。
• 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
• From <i>α</i>‐1,2‐Anhydrosugars to <i>C</i>‐Glycosides: The Influence of Lewis Acids and Nucleophiles on the Stereochemistry
  作者：Michiel A. Leeuwenburgh、Gijsbert A. van der Marel、Herman S. Overkleeft、Jacques H. van Boom

  DOI：10.1081/car-120026458

  日期：2003.12.31

  Ring opening of the epoxide function in alpha-1,2-anhydrosugars with alkynyl zinc and titanium compounds proceeds with retention of configuration to afford alpha-C-alkynylglycosides in reasonable to good yields, while the use of the corresponding alkynyltrifluoroborates results in the formation alpha/beta mixtures. Vinyl nucleophiles predominantly afford alpha-products, whereas allyl and allenyl species almost exclusively yield beta-C-glycosides.
• 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.