2-脱氧-2-(四氯苯二甲酰亚胺基)-D-吡喃葡萄糖-1,3,4,6-四乙酸盐 | 174356-26-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-脱氧-2-(四氯苯二甲酰亚胺基)-D-吡喃葡萄糖-1,3,4,6-四乙酸盐
• 中文别名: 2-脱氧-2-(四氯邻苯二甲酰亚胺基)-D-吡喃葡萄糖-1,3,4,6-四乙酸酯
• 英文名称: 1,3,4,5-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-D-glucopyranose
• 英文别名: 1,3,4,6-tetra-O-acetyl-2-deoxy-2-(3,4,5,6-tetra-chlorophthalimido)-D-glucospyranose；1,3,4,6-tetra-O-acetyl-2-deoxy-2-(3,4,5,6-tetrachlorohthalimido)-D-glucopyranose；1,3,4,6-tetra-O-acetyl-2-deoxy-2-(3,4,5,6-tetrachlorophthalimido)-D-glucopyranose；2-Deoxy-2-(tetrachlorophthalimido)-d-；[(2R,3S,4R,5R)-3,4,6-triacetyloxy-5-(4,5,6,7-tetrachloro-1,3-dioxoisoindol-2-yl)oxan-2-yl]methyl acetate
• CAS: 174356-26-4
• 化学式: C₂₂H₁₉Cl₄NO₁₁
• 分子量: 615.205
• InChiKey: PAJWAARTNUUTKR-XCRQVKOOSA-N

物化性质

• 沸点：
  676.7±55.0 °C(Predicted)
• 密度：
  1.62±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  38
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  152
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2-脱氧-2-(四氯苯二甲酰亚胺基)-D-吡喃葡萄糖-1,3,4,6-四乙酸盐 在 偶氮二异丁腈 、 氢溴酸 作用下， 以 溶剂黄146 、 苯 为溶剂， 反应 14.0h， 生成 5-acetamido-6,7,9-tri-O-acetyl-4,8-anhydro-1,2,3,5-tetradeoxy-D-glycero-D-ido-non-enitol
  参考文献：
  名称：

  Synthesis of β-C-Glycosides of N-Acetylglucosamine via Keck Allylation Directed by Neighboring Phthalimide Groups

  摘要：

  DOI：

  10.1021/jo960819o
• 作为产物：
  描述：

  四氯苯二甲酸酐 在 吡啶 、 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 2-脱氧-2-(四氯苯二甲酰亚胺基)-D-吡喃葡萄糖-1,3,4,6-四乙酸盐
  参考文献：
  名称：

  Differently N-protected 3,4,6-tri-O-acetyl-2-amino-2-deoxy-d-glucopyranosyl chlorides and their application in the synthesis of diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside

  摘要：

  Four differently N-protected 3,4,6-tri-O-acetyl-2-amino-2-deoxy-D-glucopyranosyl chlorides were synthesized and used as glycosyl donors in reactions with diosgenin. The following amine group protections were tested: trifluoroacetyl (TFA), 2,2,2-trichloroethoxycarbonyl (Troc), phthaloyl (Phth), and tetrachlorophthaloyl (TCP). Products of glycosylation were deprotected to yield diosgenyl 2-amino-2-deoxy-beta-D-glucopyranoside. The efficiency of the procedures is discussed. Additionally, a single-crystal X-ray diffraction analysis for 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranosyl chloride is reported. Orientations of the pyranose substituents as well as the planarity of the acetoxy and phthalimide groups in the crystal lattice are discussed. Structural evidence is presented for a mesomeric effect in both groups. The preference of the cis over trans orientation of the acetoxy group is confirmed in the crystal lattice. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2012.11.020

文献信息

• Synthesis of 5-Fluoro <i>N</i>-Acetylglucosamine Glycosides and Pyrophosphates via Epoxide Fluoridolysis:  Versatile Reagents for the Study of Glycoconjugate Biochemistry
  作者：Matthew C. T. Hartman、James K. Coward

  DOI：10.1021/ja0127234

  日期：2002.8.1

  catalysis via stabilization of positive charges on or near the C-1, C-4, C-5, or C-6 positions. Substrate analogues differing only in the substitution of a fluorine for the axial C-5 hydrogen would possess reduced electron density at these positions and could be useful mechanistic probes of these enzymes. Introduction of this 5-fluoro substituent after radical halogenation was problematic because of the incompatibility

  许多碳水化合物加工酶通过稳定 C-1、C-4、C-5 或 C-6 位置上或附近的正电荷来促进催化。仅在氟取代轴向 C-5 氢方面不同的底物类似物将在这些位置具有降低的电子密度，并且可能是这些酶的有用机械探针。在自由基卤化后引入这种 5-氟取代基是有问题的，因为许多保护基团与自由基卤化的不相容性以及随后的 5-氟己糖胺的不稳定性。因此，为了方便地获得各种 5-氟糖苷和糖基磷酸酯，开发了一种引入 5-氟基团的通用方法，关键步骤是 C-5, 6 环氧化物的氟化解。通过使用这种方法，已经合成了两种氟化碳水化合物，尿苷 5'-二磷酸-5-氟-N-乙酰氨基葡萄糖和辛基 5-氟-N-乙酰氨基葡萄糖。这些化合物的初步生化研究表明，5-氟类似物是几种酶催化反应中过渡态电荷发展的有用探针。
• Sulfur–Sulfur-Based Ligands Derived fromD-Sugars: Synthesis of PdII Complexes, Application in Palladium-Catalyzed Allylic Alkylation for the Synthesis of Both Members of Enantiomer Pairs, and Structural Studies
  作者：Noureddine Khiar、Cristina Serrano Araújo、Bélen Suárez、Inmaculada Fernández

  DOI：10.1002/ejoc.200500651

  日期：2006.4

  A divergent synthetic approach for the synthesis of optically pure bis(thioglycosides) of type I is reported. A common chiral intermediate with up to eight free hydroxy groups is obtained in only two steps, and from this common intermediate a large number of ligands can be synthesized. A strategy resembling positional scanning enabled the rapid discovery of an efficient catalyst for the palladium-catalyzed

  报道了一种用于合成 I 型光学纯双（硫糖苷）的不同合成方法。只需两步即可获得具有多达八个游离羟基的常见手性中间体，并且可以从该常见中间体合成大量配体。类似于位置扫描的策略能够快速发现钯催化丙二酸不对称烯丙基化的有效催化剂。由于 α-D-阿拉伯糖和 β-L-半乳糖的结构相似，通过使用天然 D-糖作为催化剂前体，可以获得烯丙基化产物的两种对映异构体，其 ee 值高达 90%。用 [PdCl2(CH3CN)2] 处理几种 C2 对称双（硫糖苷）总是导致单一的非对映体 PdII 复合物。各种 PdII 配合物的动态 NMR 研究表明，由于外异头效应，在与钯配位时对硫构型存在有效的立体化学控制。讨论了基于 NMR 研究观察到的对映选择性的解释模型。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• Glycosyl Imidates, 76. Synthesis of Aryl C-Glycosides of Glucosamine
  作者：Julio C. Castro-Palomino、Richard R. Schmidt

  DOI：10.1002/jlac.199619961019

  日期：1996.10

  glucosamine donor 2 reacts with electron-rich phenol ethers 3a–c to afford aryl C-glycosides 4a–c. The N-tetrachlorophthaloyl group could be readily removed by sodium borohydride treatment and then phthalide formation or by treatment with ethylenediamine, respectively. The resulting product was subjected to reaction with acetic anhydride in pyridine to afford N,O-acetylated compounds 5a–c. After treatment

  所述Ñ -tetrachlorophthalimido保护的葡糖胺供体2种发生反应与富电子苯酚醚3A-C ，得到芳基C糖苷4a-c中。该Ñ -tetrachlorophthaloyl组可以由硼氢化钠处理，然后形成苯酞或通过处理而容易地除去与乙二胺，分别。使所得产物与乙酸酐在吡啶中反应，得到N，O-乙酰化的化合物5a–c。用乙二胺处理后，也可得到N，O-未保护的化合物，如6c所示。
• <i>N</i>-Alkyl derivatives of diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside; synthesis and antimicrobial activity
  作者：Agata Walczewska、Daria Grzywacz、Dorota Bednarczyk、Małgorzata Dawgul、Andrzej Nowacki、Wojciech Kamysz、Beata Liberek、Henryk Myszka

  DOI：10.3762/bjoc.11.97

  日期：——

  Diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside is a synthetic saponin exhibiting attractive pharmacological properties. Different pathways tested by us to obtain this glycoside are summarized here. Moreover, the synthesis of N-alkyl and N,N-dialkyl derivatives of the glucopyranoside is presented. Evaluation of antibacterial and antifungal activities of these derivatives indicates that they have no inhibitory activity against Gram-negative bacteria, whereas many of the tested N-alkyl saponins were found to inhibit the growth of Gram-positive bacteria and human pathogenic fungi.

  Diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside是一种具有吸引人的药理特性的合成皂苷。我们测试了不同的途径来获得这种糖苷，这里总结了这些途径。此外，还介绍了合成葡萄糖吡喃糖苷的N-烷基和N,N-二烷基衍生物。对这些衍生物的抗菌和抗真菌活性评估表明，它们对革兰氏阴性菌没有抑制活性，而许多经过测试的N-烷基皂苷被发现抑制了革兰氏阳性菌和人类病原真菌的生长。
• 1H and13C NMR and X-ray diffraction data for a diosgenylN,O-protected glucopyranoside
  作者：Henryk Myszka、Dorota Bednarczyk、Zbigniew Ciunik、Wies?aw Kaca

  DOI：10.1002/mrc.981

  日期：2002.3

  The assignments of 1H and 13C NMR chemical shifts together with x‐ray diffraction data for synthesized diosgenyl 3,4,6‐tri‐O‐acetyl‐2‐deoxy‐2‐tetrachlorophthalimido‐β‐D‐glucopyranoside are described. The structure of this glycoside was established by using homo‐ and heteronuclear two‐dimensional NMR techniques. X‐ray diffraction data for this compound are also reported. Copyright © 2002 John Wiley

  描述了合成的二萜基 3,4,6-三-O-乙酰基-2-脱氧-2-四氯邻苯二甲酰亚胺-β-D-吡喃葡萄糖苷的 1H 和 13C NMR 化学位移以及 X 射线衍射数据。该糖苷的结构是通过使用同核和异核二维核磁共振技术确定的。还报告了该化合物的 X 射线衍射数据。版权所有 © 2002 John Wiley & Sons, Ltd.