cyclohexyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside | 160412-84-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cyclohexyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside
• 英文别名: (2R,3R,4R,5R,6R)-2-cyclohexyloxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-ol
• CAS: 160412-84-0
• 化学式: C₃₃H₄₀O₆
• 分子量: 532.677
• InChiKey: CNLWUDZFXACMQR-YKNMHBIISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  39
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  cyclohexyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside 在 palladium on activated charcoal 吡啶 、 sodium tetrahydroborate 、 氢气 、 乙酸酐 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 二甲基亚砜 为溶剂， 生成 cyclohexyl 2,3,4,6-tetra-O-acetyl-β-D-mannopyranoside
  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：

  cyclohexyl 3,4,6-tri-O-benzyl-2-O-(2,2-dimethyltrimethylene phosphonoyl)-β-D-glucopyranoside 在 sodium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 反应 1.0h， 以95%的产率得到cyclohexyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  磷酸二烷基酯作为寡糖合成中的立体定向保护基。

  摘要：

  DOI：

  10.1002/anie.200602699

文献信息

• N-Iodosuccinimide-mediated intramolecular aglycon delivery
  作者：S.C Ennis、A.J Fairbanks、C.A Slinn、R.J Tennant-Eyles、H.S Yeates

  DOI：10.1016/s0040-4020(01)00308-8

  日期：2001.5

  via Tebbe methylenation of either 2-O acetates or para-methoxybenzoates. N-Iodosuccinimide may then be employed to achieve both tethering and thioglycoside activation allowing the stereoselective synthesis of α-glucosides and β-mannosides, either in a one or two step procedure.

  烯醇醚可以通过2- O乙酸酯或对-甲氧基苯甲酸酯的Tebbe甲基化来获得。然后可以使用N-碘代琥珀酰亚胺来实现束缚和硫糖苷活化两者，从而允许以一或两个步骤的方式立体选择性地合成α-葡糖苷和β-甘露糖苷。
• 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。
• 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
• Silica gel-catalyzed β-O-glucosylation of alcohols with 1,2-anhydro-3,4,6-tri-O-pivaloyl-α-d-glucopyranose
  作者：Yoh-ichi Matsushita、Kazuhiro Sugamoto、Yoshio Kita、Takanao Matsui

  DOI：10.1016/s0040-4039(97)10315-x

  日期：1997.12

  1,2-Anhydro-3,4,6-tri-O-pivaloyl-alpha-D-glucopyranose (1a) was allowed to react with alcohols in the presence of solid acids such as silica gel and zeolite HY, to afford beta-O-glucosides stereoselectively. Several natural glucosides were synthesized by the application of the present reaction. (C) 1997 Elsevier Science Ltd.
• Dialkylphosphates as Stereodirecting Protecting Groups in Oligosaccharide Synthesis
  作者：Takeshi Yamada、Kazunobu Takemura、Jun-ichi Yoshida、Shigeru Yamago

  DOI：10.1002/anie.200602699

  日期：2006.11.20