methyl 2,4,6-tri-O-benzyl-α-D-mannopyranoside | 73045-58-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,4,6-tri-O-benzyl-α-D-mannopyranoside
• 英文别名: (2S,3S,4S,5S,6R)-2-methoxy-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-ol
• CAS: 73045-58-6
• 化学式: C₂₈H₃₂O₆
• 分子量: 464.558
• InChiKey: UFTIKUYXMPCFQZ-VFHRMQJUSA-N

物化性质

• 沸点：
  608.7±55.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  methyl 2,4,6-tri-O-benzyl-α-D-mannopyranoside 在 palladium on activated charcoal 4 A molecular sieve 、 氢气 、 sodium methylate 、 氰化汞 、 mercury dibromide 作用下， 以 甲醇 、 乙醇 、 溶剂黄146 、 乙腈 为溶剂， 25.0 ℃ 、350.0 kPa 条件下， 反应 8.0h， 生成 甲基 3-O-alpha-D-甘露糖基-alpha-D-吡喃甘露糖苷
  参考文献：
  名称：

  Lysosomal-enzyme targeting: the phosphorylation of synthetic d-mannosyl saccharides by UDP-N-acetylglucosamine:lysosomal-enzyme N-acetylglucosaminephosphotransferase from rat-liver microsomes and fibroblasts

  摘要：

  Phosphorylation of the D-mannose residues of lysosomal enzymes is essential for the uptake and intracellular transport of these enzymes to lysosomes. The GlcNAc-P-transferase which is involved in the phosphorylation reaction seems to recognize a signal, probably a protein conformation, common to many lysosomal enzymes. To evaluate the role of the carbohydrate portion of the enzyme in these phosphorylation reactions, the acceptor specificity of GlcNAc-P-transferase from rat-liver microsomes and fibroblasts was examined with the aid of synthetic D-mannosyl disaccharides and derivatives that are closely related to the high-mannose type of oligosaccharides. Four methyl D-mannobiosides were synthesized, and their structures were established by 13C-n.m.r. spectroscopy. Of all the D-mannosyl saccharides tested, alpha-D-Man-(1----2)-alpha-D-Man-(1----OMe) was found to be the best acceptor, thereby suggesting that oligosaccharide structure may also have a role to play in recognition by this enzyme.

  DOI：

  10.1016/s0008-6215(00)90298-2
• 作为产物：
  描述：

  甲基-D-丙噻 在 四丁基碘化铵 、 sodium hydride 、 二正丁基氧化锡 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 为溶剂， 反应 129.0h， 生成 methyl 2,4,6-tri-O-benzyl-α-D-mannopyranoside
  参考文献：
  名称：

  制备稳定的鸟粪膦类似物的高级中间体的制备

  摘要：

  描述了C-甘露糖基-鸟苷23的合成，C-甘露糖基-鸟苷23是用于制备鸟嘌呤霉素稳定类似物的高级中间体。该收敛方法的特征在于改进的8-取代鸟嘌呤的Traube型合成，然后进行核糖基化。NMR研究表明，23的C- mannopyranosyl部分采用扭曲的1 C 4构象，而核苷则主要为顺取向。

  DOI：

  10.1002/hlca.200490118

文献信息

• A Simple Synthesis of Methyl 2,3,6- and 2,4,6-Tri-<i>O</i>-benzyl-α-D-mannosides
  作者：Shinkiti Koto、Kazuhiro Takenaka、Naohiko Morishima、Akiko Sugimoto、Shonosuke Zen

  DOI：10.1246/bcsj.57.3603

  日期：1984.12

  Cotrolled benzylation of methyl α-D-mannopyranoside with benzyl chloride and LiOH selectively gave the 2,3,6-tribenzyl ether in a 53% yield. Such a reaction using benzyl chloride and KOH afforded mainly the 2,4,6-tribenzyl ether in a 41% yield. The products were allylated and then hydrolyzed to give the corresponding 1-OH derivatives.

  用苄基氯和 LiOH 控制甲基 α-D-吡喃甘露糖苷的苄基化反应，选择性地得到 2,3,6-三苄基醚，产率为 53%。使用苄基氯和KOH的这种反应主要以41%的产率提供2,4,6-三苄基醚。产物被烯丙基化，然后水解得到相应的1-OH衍生物。
• An Easy and Versatile Approach for the Regioselective De-O-benzylation of Protected Sugars Based on the I2/Et3SiH Combined System
  作者：Antonello Pastore、Silvia Valerio、Matteo Adinolfi、Alfonso Iadonisi

  DOI：10.1002/chem.201003332

  日期：2011.5.16

  whereas the regioselectivity appears to be mainly controlled by steric effects. However, the presence of an electron withdrawing acyl protecting group can switch the regioselectivity to favour deprotection of the carbinol position farthest from the ester group. The protocol is experimentally simple and provides straightforward access in useful yields to a wide range of partially protected mono‐ and disaccharide

  使用便宜且易于处理的试剂，例如I 2和Et 3SiH在低温下可以从高度O-苄基化的碳水化合物中区域选择性地除去苄基保护基团。观察到的区域选择性取决于前体的性质，最难获得的甲醇经常被释放出来。机理研究表明，原位产生的HI是该过程的促进剂，而区域选择性似乎主要受空间效应控制。然而，吸电子酰基保护基的存在可以切换区域选择性，以促进最远离酯基的甲醇位置的脱保护。该协议在实验上很简单，可以以有用的收率直接访问各种部分受保护的单糖和二糖结构单元，这些单元对于合成生物学上有用的寡糖或高度官能化的手性化合物都具有重要意义。如此获得的部分受保护的糖也可以与糖基供体原位偶联，如从完全受保护的前体一锅法合成Lewis X模拟物所示。
• <i>N</i> -Trifluoromethylthiosaccharin/TMSOTf: A New Mild Promoter System for Thioglycoside Activation
  作者：Cian Mc Carthy、Matthias Tacke、Xiangming Zhu

  DOI：10.1002/ejoc.201900265

  日期：2019.4.30

  N‐Trifluoromethylthiosaccharin was used to activate a series of thioglycosides in the presence of catalytic amounts of TMSOTf. Chemoselective activation of ethyl thioglycosides in the presence of phenyl thioglycosides was also achieved under the same conditions.

  在催化量的TMSOTf存在下，N-三氟甲基硫代糖精用于活化一系列硫糖苷。在相同条件下，在苯基硫代糖苷的存在下，也能实现乙基硫代糖苷的化学选择性活化。
• Oxidative Activation of C–S Bonds with an Electropositive Nitrogen Promoter Enables Orthogonal Glycosylation of Alkyl over Phenyl Thioglycosides
  作者：Annabel Kitowski、Ester Jiménez-Moreno、Míriam Salvadó、Jordi Mestre、Sergio Castillón、Gonzalo Jiménez-Osés、Omar Boutureira、Gonçalo J. L. Bernardes

  DOI：10.1021/acs.orglett.7b02886

  日期：2017.10.6

  method for the selective activation of thioglycosides that uses the N+-thiophilic reagent O-mesitylenesulfonylhydroxylamine (MSH) as a promoter is presented. The reaction proceeds via anomeric mesitylensulfonate intermediates, which could be isolated and fully characterized by placing a fluorine atom at the C2 position. In the presence of a soft Lewis acid, glycosylation reaction proceeds at ambient temperature

  提出了一种选择性活化硫糖苷的方法，该方法使用N +-亲硫试剂O-均三甲苯磺酰基羟胺（MSH）作为促进剂。该反应通过异戊基均磺酸磺酸盐中间体进行，该中间体可以被分离并且可以通过将氟原子置于C 2位来充分表征。在软路易斯酸的存在下，糖基化反应在环境温度下以良好的产率进行。进一步证明，在S-苯基供体的存在下可以正交活化S-乙基，从而可以设计顺序糖基化策略。
• Ceric ammonium nitrate/acetic anhydride: A tunable system for the <i>O</i>-acetylation and mononitration of diversely protected carbohydrates
  作者：Mohindra Seepersaud、Savita Seecharan、Lorale J. Lalgee、Nigel Kevin Jalsa

  DOI：10.1080/00397911.2016.1230219

  日期：2017.5.3

  ABSTRACT Esterification of a wide range of partially protected carbohydrate derivatives was achieved using acetic anhydride and a catalytic amount of ceric ammonium nitrate (CAN). Compatibility with the commonly used protecting groups was demonstrated, with the esterified products being furnished in good yields. Apart from affording the O-acetylated products, their mononitrated counterparts were also

  摘要 使用乙酸酐和催化量的硝酸铈铵 (CAN) 实现了多种部分保护的碳水化合物衍生物的酯化。证明了与常用保护基团的相容性，酯化产物以良好的产率提供。除了提供 O-乙酰化产物外，还产生了它们的单硝化对应物，这取决于起始材料的反应性。降低 CAN 的摩尔当量只能提供 O-乙酰化产物，而增加它有利于单硝化衍生物。图形概要