methyl 4,6-O-para-nitrobenzylidene-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 4,6-O-para-nitrobenzylidene-α-D-glucopyranoside
• 英文别名: methyl-4,6-O-(p-nitrobenzylidene)-α-D-glucopyranoside；methyl 4,6-O-[(4-nitrophenyl)methylene]-α-D-glucopyranoside；(4aR,6S,7R,8R,8aS)-6-methoxy-2-(4-nitrophenyl)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-7,8-diol
• 化学式: C₁₄H₁₇NO₈
• 分子量: 327.291
• InChiKey: QDGVVAPLJLTAKK-BTZLDLHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  123
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-para-nitrobenzylidene-α-D-glucopyranoside 在 dipotassium hydrogenphosphate 、 tris(triphenylphosphine)ruthenium(II) chloride 、 甲基硼酸 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以31%的产率得到methyl-4,6-O-(p-nitrobenzylidene)-α-D-mannopyranoside
  参考文献：
  名称：

  Ru(II) 催化和硼介导的 1,2-反式二醇选择性差向异构化合成稀有糖的一般策略为 1,2-顺式二醇

  摘要：

  人聚糖主要由九种常见的糖组成部分组成。另一方面，已经在细菌中发现了数百种单糖，其中大多数不易获得。获得这些稀有糖和相应的糖缀合物的能力可以促进对细菌中各种重要的生物学过程的研究，包括微生物群与人类宿主之间的相互作用。许多稀有糖也存在于各种具有显着生物活性的天然产物和药物试剂中。尽管已经开发了几种用于合成稀有单糖的方法，但其中大多数都涉及冗长的步骤。在此处，反式二醇到 1,2-顺式二醇。硼酸酯的形成将平衡推向 1,2-顺式二醇产物，该产物可立即用于进一步的选择性功能化和糖基化。通过在天然产物或生物活性化合物中有效构建糖苷骨架，证明了该策略的实用性。

  DOI：

  10.1021/jacs.1c13399
• 作为产物：
  描述：

  对硝基苯甲醛 、 alpha-甲基葡萄糖甙 在 硫酸 作用下， 反应 2.0h， 以77%的产率得到methyl 4,6-O-para-nitrobenzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Directing-protecting groups for carbohydrates. Design, conformational study, synthesis and application to regioselective functionalization

  摘要：

  A novel concept of regioselective transformation of secondary hydroxyl groups in carbohydrates is presented. First, the relative reactivity of the free hydroxyl groups of onoprotected D-glucose derivatives was assessed using acetylation as a model reaction. As a result, acylation of these polyols gave it mixture of monosubstituted products in which the 3-O functionalized derivatives predominated. Novel hydrogen bond acceptor protecting groups were next designed to modulate the 4-OH and 3-OH reactivity in the hope to mediate higher regioselective transformations. A molecular modeling study later validated by spectroscopic analysis predicted additional intramolecular hydrogen bonds between the hydroxyl groups and pyridyl-containing protecting groups. Taking advantage of this induced hydrogen bond network. we achieved regioselective acetylation of the hydroxyl group at position 3 without protecting any secondary hydroxyl groups of the carbohydrate moiety. This designed protecting/directing group increased the nucleophilicity and the steric hindrance of position 3. As a result, optimization of the reaction conditions enabled the monoacetylation (not affected by steric hindrance) of 6-O-protected,glucopyranosides at position 3 and selective silylation (affected by steric hindrance) of position 2 in high isolated yields and regioselectivities. This result certainly opens doors to the regioselective open glycosylation of carbohydrates. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.04.060

文献信息

• Directing/protecting groups mediate highly regioselective glycosylation of monoprotected acceptors
  作者：Janice Lawandi、Sylvain Rocheleau、Nicolas Moitessier

  DOI：10.1016/j.tet.2011.07.026

  日期：2011.10

  A directing/protecting group designed for regioselective functionalization of partially-protected glucopyrannosides has been successfully used to prepare disaccharides in high yields. Most importantly, it has been demonstrated that highly regioselective and stereoselective glycosylation can be achieved when disarmed donors are employed. This study demonstrates the ability of directing/protecting group to induce regioselective glycosylation of carbohydrates and opens the field to the design of other DPGs for other monosaccharides. (C) 2011 Elsevier Ltd. All rights reserved.
• Site-Selective Acylation of Carbohydrates Directed by Recyclable Polymer-Supported Isothiourea Catalysts
  作者：Wang-Ze Song、Yu-Bin Zheng、Jun-Hao Li、Ming Li、Kun Dong、Karim Ullah

  DOI：10.3987/com-18-14025

  日期：——

  The polystyrene-supported isothiourea catalysts, derived from the homogeneous catalyst BTMs, were synthesized and applied to the site-selective acylation of carbohydrates. The catalysts can be recovered and reused conveniently for 10 cycles without significantly loss in either activity or selectivity. It offers a sustainable and environmentally benign approach for the site-selective functionalization of carbohydrates.
• Gronwald, Oliver; Shinkai, Seiji, Journal of the Chemical Society. Perkin Transactions 2 (2001), 2001, # 10, p. 1933 - 1937
  作者：Gronwald, Oliver、Shinkai, Seiji

  DOI：——

  日期：——
• Directing-protecting groups for carbohydrates. Design, conformational study, synthesis and application to regioselective functionalization
  作者：Nicolas Moitessier、Pablo Englebienne、Yves Chapleur

  DOI：10.1016/j.tet.2005.04.060

  日期：2005.7

  A novel concept of regioselective transformation of secondary hydroxyl groups in carbohydrates is presented. First, the relative reactivity of the free hydroxyl groups of onoprotected D-glucose derivatives was assessed using acetylation as a model reaction. As a result, acylation of these polyols gave it mixture of monosubstituted products in which the 3-O functionalized derivatives predominated. Novel hydrogen bond acceptor protecting groups were next designed to modulate the 4-OH and 3-OH reactivity in the hope to mediate higher regioselective transformations. A molecular modeling study later validated by spectroscopic analysis predicted additional intramolecular hydrogen bonds between the hydroxyl groups and pyridyl-containing protecting groups. Taking advantage of this induced hydrogen bond network. we achieved regioselective acetylation of the hydroxyl group at position 3 without protecting any secondary hydroxyl groups of the carbohydrate moiety. This designed protecting/directing group increased the nucleophilicity and the steric hindrance of position 3. As a result, optimization of the reaction conditions enabled the monoacetylation (not affected by steric hindrance) of 6-O-protected,glucopyranosides at position 3 and selective silylation (affected by steric hindrance) of position 2 in high isolated yields and regioselectivities. This result certainly opens doors to the regioselective open glycosylation of carbohydrates. (c) 2005 Elsevier Ltd. All rights reserved.
• General Strategy for the Synthesis of Rare Sugars via Ru(II)-Catalyzed and Boron-Mediated Selective Epimerization of 1,2-<i>trans</i>-Diols to 1,2-<i>cis</i>-Diols
  作者：Xiaolei Li、Jicheng Wu、Weiping Tang

  DOI：10.1021/jacs.1c13399

  日期：2022.3.2

  Although several methods have been developed for the synthesis of rare monosaccharides, most of them involve lengthy steps. Herein, we report an efficient and general strategy that can provide access to rare sugars from commercially available common monosaccharides via a one-step Ru(II)-catalyzed and boron-mediated selective epimerization of 1,2-trans-diols to 1,2-cis-diols. The formation of boronate esters

  人聚糖主要由九种常见的糖组成部分组成。另一方面，已经在细菌中发现了数百种单糖，其中大多数不易获得。获得这些稀有糖和相应的糖缀合物的能力可以促进对细菌中各种重要的生物学过程的研究，包括微生物群与人类宿主之间的相互作用。许多稀有糖也存在于各种具有显着生物活性的天然产物和药物试剂中。尽管已经开发了几种用于合成稀有单糖的方法，但其中大多数都涉及冗长的步骤。在此处，反式二醇到 1,2-顺式二醇。硼酸酯的形成将平衡推向 1,2-顺式二醇产物，该产物可立即用于进一步的选择性功能化和糖基化。通过在天然产物或生物活性化合物中有效构建糖苷骨架，证明了该策略的实用性。