methyl 2-azido-3,4-di-O-benzyl-2-deoxy-α-D-glucopyranoside | 352547-12-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-azido-3,4-di-O-benzyl-2-deoxy-α-D-glucopyranoside
• 英文别名: [(2R,3S,4R,5R,6S)-5-azido-6-methoxy-3,4-bis(phenylmethoxy)oxan-2-yl]methanol
• CAS: 352547-12-7
• 化学式: C₂₁H₂₅N₃O₅
• 分子量: 399.447
• InChiKey: DGQQGHISWOSILJ-ONUIULTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  71.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 2-azido-3,4-di-O-benzyl-2-deoxy-α-D-glucopyranoside 在 20% palladium hydroxide-activated charcoal 、 氢气 、 三甲基铵三氧化硫共聚物 作用下， 以 aq. phosphate buffer 、 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 methyl 2-amino-2-deoxy-6-O-sulfonato-α-D-glucopyranoside
  参考文献：
  名称：

  Glycans as Ligands in Bioinorganic Chemistry. Probing the Interaction of a Trinuclear Platinum Anticancer Complex with Defined Monosaccharide Fragments of Heparan Sulfate

  摘要：

  We report herein a detailed NMR study of the aquation and subsequent covalent binding of the trinuclear clinical agent [{trans-PtCl((NH3)-N-15)(2)}(2){mu-trans-Pt((NH3)-N-15)(2)((NH2)-N-15(CH2)(6)(NH2)-N-15)(2)}](4+) (1, 1,0,1/t,t,t or Triplatin) with three d-glucosamine residues containing varied O-sulfate and N-sulfate or N-acetyl substitutions, which represent monosaccharide fragments present within the repeating disaccharide sequences of cell surface heparan sulfate (HS). The monosaccharides GlcNS(6S), GlcNS, and GlcNAc(6S) were synthesized in good yield from a common 4,6-diol alpha-methyl glucopyranoside intermediate. The reactions of N-15-1 with sodium sulfate, GlcNS(6S), GlcNS, and GlcNAc(6S) were followed by 2D [H-1,N-15] heteronuclear single quantum coherence (HSQC) NMR spectroscopy using conditions (298 K, pH approximate to 5.4) similar to those previously used for other anionic systems, allowing for a direct comparison. The equilibrium constants (pK(1)) for the aquation of 1 in the presence of GlcNS(6S) and GlcNS were slightly higher compared to that of the aquation in a sulfate solution, while a comparable pK(1) value was observed in the presence of GlcNAc(6S). A comparison of the rate constants for sulfate displacement of the aqua ligand showed preferential binding to 2-N-sulfate compared to 6-O-sulfate but a more rapid liberation. For disulfated GlcNS(6S), equilibrium conditions were achieved rapidly (9 h) and strongly favored the dichloro form, with <2% sulfato species observed. The value of k(L1) was up to 15-fold lower than that for binding to sulfate, whereas the rate constant for the reverse ligation (k(-L1)) was comparable. Equilibrium conditions were achieved much more slowly (similar to 100 h) for the reactions of 1 with GlcNS and GlcNAc(6S), attributed to covalent binding also to the N-donor of the sulfamate (GlcNS) group and the O-donor of the N-acetyl [GlcNAc(6S)] group. The rate constants (k(L2)) were 20-40-fold lower than that for binding to the 2-N- or 6-O-sulfate, but the binding was less reversible, so that their equilibrium concentrations (5-8%) were comparable to the 2-N- or 6-O-sulfate-bound species. The results emphasize the relevance of glycans in bioinorganic chemistry and underpin a fundamental molecular description of the HS-Pt interactions that alter the profile of platinum agents from cytotoxic to metastatic in a systematic manner.

  DOI：

  10.1021/acs.inorgchem.8b03035
• 作为产物：
  描述：

  Methyl 2-azido-3-O-benzyl-6-O-tert-butyldiphenylsilyl-2-deoxy-alpha-D-glucopyranoside 在 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 24.0h， 生成 methyl 2-azido-3,4-di-O-benzyl-2-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  Glycans as Ligands in Bioinorganic Chemistry. Probing the Interaction of a Trinuclear Platinum Anticancer Complex with Defined Monosaccharide Fragments of Heparan Sulfate

  摘要：

  We report herein a detailed NMR study of the aquation and subsequent covalent binding of the trinuclear clinical agent [{trans-PtCl((NH3)-N-15)(2)}(2){mu-trans-Pt((NH3)-N-15)(2)((NH2)-N-15(CH2)(6)(NH2)-N-15)(2)}](4+) (1, 1,0,1/t,t,t or Triplatin) with three d-glucosamine residues containing varied O-sulfate and N-sulfate or N-acetyl substitutions, which represent monosaccharide fragments present within the repeating disaccharide sequences of cell surface heparan sulfate (HS). The monosaccharides GlcNS(6S), GlcNS, and GlcNAc(6S) were synthesized in good yield from a common 4,6-diol alpha-methyl glucopyranoside intermediate. The reactions of N-15-1 with sodium sulfate, GlcNS(6S), GlcNS, and GlcNAc(6S) were followed by 2D [H-1,N-15] heteronuclear single quantum coherence (HSQC) NMR spectroscopy using conditions (298 K, pH approximate to 5.4) similar to those previously used for other anionic systems, allowing for a direct comparison. The equilibrium constants (pK(1)) for the aquation of 1 in the presence of GlcNS(6S) and GlcNS were slightly higher compared to that of the aquation in a sulfate solution, while a comparable pK(1) value was observed in the presence of GlcNAc(6S). A comparison of the rate constants for sulfate displacement of the aqua ligand showed preferential binding to 2-N-sulfate compared to 6-O-sulfate but a more rapid liberation. For disulfated GlcNS(6S), equilibrium conditions were achieved rapidly (9 h) and strongly favored the dichloro form, with <2% sulfato species observed. The value of k(L1) was up to 15-fold lower than that for binding to sulfate, whereas the rate constant for the reverse ligation (k(-L1)) was comparable. Equilibrium conditions were achieved much more slowly (similar to 100 h) for the reactions of 1 with GlcNS and GlcNAc(6S), attributed to covalent binding also to the N-donor of the sulfamate (GlcNS) group and the O-donor of the N-acetyl [GlcNAc(6S)] group. The rate constants (k(L2)) were 20-40-fold lower than that for binding to the 2-N- or 6-O-sulfate, but the binding was less reversible, so that their equilibrium concentrations (5-8%) were comparable to the 2-N- or 6-O-sulfate-bound species. The results emphasize the relevance of glycans in bioinorganic chemistry and underpin a fundamental molecular description of the HS-Pt interactions that alter the profile of platinum agents from cytotoxic to metastatic in a systematic manner.

  DOI：

  10.1021/acs.inorgchem.8b03035

文献信息

• Stereoselective Iterative One-Pot Synthesis of <i>N</i>-Glycolylneuraminic Acid-Containing Oligosaccharides
  作者：David Crich、Baolin Wu

  DOI：10.1021/ol801548k

  日期：2008.9.18

  The use of an N-acyloxazolidinone-protected S-adamantanyl thiosialoside allows the highly stereoselective, one-pot multicomponent synthesis of alpha-sialoside-based oligosaccharides.

  使用 N-酰基恶唑烷酮保护的 S-金刚烷基硫代唾液酸允许高度立体选择性、一锅多组分合成基于 α-唾液酸苷的寡糖。
• Metal Trifluoromethanesulfonate-Catalyzed Regioselective Reductive Ring Opening of Benzylidene Acetals
  作者：Chi-Rung Shie、Zheng-Hao Tzeng、Cheng-Chung Wang、Shang-Cheng Hung

  DOI：10.1002/jccs.200900076

  日期：2009.6

  study of various metal trifluoromethanesulfonates as efficient catalysts in the regioselective reductive ring opening of benzylidene acetals is described, including the effects of solvents, reducing agents, and temperature. These catalysts are found to be effective in cleaving the 4,6‐O‐acetal rings of hexopyranosides at either O4 or O6, respectively. When used in conjunction with a 1 M solution of

  系统地研究了各种金属三氟甲磺酸盐作为亚苄基乙缩醛的区域选择性还原开环中的有效催化剂，包括溶剂，还原剂和温度的影响。发现这些催化剂可有效裂解六吡喃糖苷在O4或O6处的4,6- O-乙缩醛环。与1M BH 3溶液一起使用时·THF中的THF无需额外添加任何溶剂，它会影响O6位置的环裂变以生成相应的伯醇，而在乙腈中以二甲基乙基硅烷作为还原剂存在会导致O4的开环，从而导致生成仲羟基衍生物高选择性和高收率。这些方法可以应用于包含各种官能团的多种基材。
• Stereocontrolled Synthesis of the Equatorial Glycosides of 3-Deoxy-<scp>d</scp>-manno-oct-2-ulosonic Acid: Role of Side Chain Conformation
  作者：Philemon Ngoje、David Crich

  DOI：10.1021/jacs.0c03215

  日期：2020.4.29

  relationship of the bacterial sialic acid, pseudaminic acid, and 3-Deoxy-D-manno-oct-2-ulosonic acid (KDO) affords the hypothesis that suitably protected KDO donors will adopt the trans,gauche conformation of their side chain and consequently be highly equatorially selective in their coupling reac-tions conducted at low temperature. This hypothesis is borne out by the synthesis, conformational analysis, and

  细菌唾液酸、伪胺酸和 3-Deoxy-D-manno-oct-2-ulosonic acid (KDO) 的假对称关系提供了这样一个假设，即适当保护的 KDO 供体将采用其侧链的反式、gauche 构象和因此，它们在低温下进行的耦合反应中具有高度的赤道选择性。这一假设得到了在 -78 °C 下在二氯甲烷中偶联全-O-乙酰基或苄基保护的 KDO 供体时所见的合成、构象分析和出色的赤道选择性所证实。对糖基化反应的机理理解正在推进到可以进行选择性预测的阶段。在这种情况下，
• Cu(OTf)2 as an Efficient and Dual-Purpose Catalyst in the Regioselective Reductive Ring Opening of Benzylidene Acetals
  作者：Chi-Rung Shie、Zheng-Hao Tzeng、Suvarn S. Kulkarni、Biing-Jiun Uang、Ching-Yun Hsu、Shang-Cheng Hung

  DOI：10.1002/anie.200462172

  日期：2005.3.4
• Homologation of methyl 2-azido- and 2-acetamido-3,4-di-O-benzyl-2-deoxy-d-hexopyranosides with allyloxymethylmagnesium chloride
  作者：Barbara Grzeszczyk、Aleksander Zamojski

  DOI：10.1016/s0008-6215(01)00078-7

  日期：2001.5

  Methyl 2-azido-2-deoxy-hexodialdo-1,5-pyranosides of the alpha-, beta -D-gluco and alpha -D-manno configuration as well as methyl 2-acetamido-2-deoxy-hexodialdo-1,5-pyranosides of the alpha- and beta -D-gluco configuration, protected at positions 3 and 4 with O-benzyl groups were reacted with an excess of allyloxymethylmagnesium or (phenyldimethylsilyl)methylmagnesium chlorides to afford mixtures of C-6 stereoisomeric heptopyranosides. Configuration of the products separated by column chromatography was assigned by H-1 NMR data. (C) 2001 Elsevier Science Ltd. All rights reserved.