1,3,4,6-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α-D-glucopyranoside | 183388-13-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,3,4,6-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α-D-glucopyranoside
• 英文别名: 2-Deoxy-2-(tetrachlorophthalimido)-D-glucopyranose 1,3,4,6-tetraacetate；[(2R,3S,4R,5R,6R)-3,4,6-triacetyloxy-5-(4,5,6,7-tetrachloro-1,3-dioxoisoindol-2-yl)oxan-2-yl]methyl acetate
• CAS: 183388-13-8
• 化学式: C₂₂H₁₉Cl₄NO₁₁
• 分子量: 615.205
• InChiKey: PAJWAARTNUUTKR-DRLSZQQQSA-N

物化性质

• 熔点：
  194 °C(Solv: ethanol (64-17-5))
• 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：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α-D-glucopyranoside 在 氢溴酸 、 溶剂黄146 作用下， 生成 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α-D-glucopyranosyl bromide
  参考文献：
  名称：

  Access to tetrachlorophthalimide-protected ethyl 2-amino-2-deoxy-1-thio-β-d-glucopyranosides

  摘要：

  Ethyl 2-deoxy-2-tetrachlorophthalimido-1-thio-beta-D-glucopyranoside (7) was prepared from glucosamine hydrochloride in four steps with a 20-25% overall yield. Formation of 1,3,4,6-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranoside (5) was found to be crucial for this reaction sequence since the corresponding alpha-1-acetate did not react in Lewis-acid-catalyzed ethylthio glycosidations. Formation of the beta-1-acetate (5) was achieved by treatment of 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-alpha-D-glucopyranosol bromide(4) with acetic acid under silver zeolite promotion. This was necessary because conditions normally used for p-l-acetate formation were not tolerated by the tetrachlorophthalimido (TCP) group. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(98)00309-7
• 作为产物：
  描述：

  2-氨基-2-脱氧葡萄糖盐酸盐 在 吡啶 、 sodium methylate 、 三乙胺 作用下， 以 甲醇 为溶剂， 反应 16.83h， 生成 1,3,4,6-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α-D-glucopyranoside
  参考文献：
  名称：

  氨基磺酸糖基酯76.氨基葡萄糖的芳基C-糖苷的合成†

  摘要：

  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。

  DOI：

  10.1002/jlac.199619961019

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。
• Synthesis of <i>C</i> ‐Glycosyl Amino Acid Building Blocks Suitable for the Solid‐Phase Synthesis of Multivalent Glycopeptide Mimics
  作者：Niels R. M. Reintjens、Tony S. Koemans、Nick Zilverschoon、Riccardo Castelli、Robert A. Cordfunke、Jan Wouter Drijfhout、Nico J. Meeuwenoord、Herman S. Overkleeft、Dmitri V. Filippov、Gijsbert A. Marel、Jeroen D. C. Codée

  DOI：10.1002/ejoc.202000587

  日期：2020.8.31

  C-glycosyl functionalized lysine building blocks, featuring C-glycosidic derivatives of alpha-rhamnose, alpha-mannose, alpha-galactose, beta-galactose, and beta-N-acetyl glucosamine have been designed and synthesized. These derivatives, equipped with acid-labile protecting groups, are eminently suitable for solid-phase synthesis of multivalent glycopeptides. The lysine building blocks were prepared fromC-allyl

  已经设计并合成了五个 C-糖基功能化赖氨酸构件，其特征是 α-鼠李糖、α-甘露糖、α-半乳糖、β-半乳糖和β-N-乙酰氨基葡萄糖的 C-糖苷衍生物。这些衍生物带有酸不稳定保护基团，非常适合多价糖肽的固相合成。赖氨酸结构单元由 C-烯丙基糖苷制备，该糖苷经历了与丙烯酸酯的 Grubbs 交叉复分解，然后还原所得 α,β-不饱和酯中的 C=C 双键，并释放羧酸酯以允许缩合带有赖氨酸侧链。将由此得到的C-糖苷共五种，用于三种糖肽的固相肽合成(SPPS)，
• N-tetrachlorophthaloyl (TCP) for ready protection/deprotection of amino sugar glycosides
  作者：John S Debenham、Sheryl D Debenham、Bert Fraser-Reid

  DOI：10.1016/s0968-0896(96)00173-3

  日期：1996.11

  The tetrachlorophthaloyl (TCP) group can be utilized when imidic protection of an amine is desired and durability of the protecting group to conditions ranging from mildly basic to harshly acidic is required. Installation can be accomplished in two steps by treating the free base with the commercially available TCP anhydride, and then closing the imidic ring with acetic anhydride and pyridine. Cleavage

  当需要胺的亚胺保护并且需要保护基团在从弱碱性到强酸性的条件下的耐久性时，可以使用四氯邻苯二甲酰基（TCP）基团。通过用市售的TCP酸酐处理游离碱，然后用乙酸酐和吡啶封闭酰亚胺环，可以分两步完成安装。在非常温和的条件下，通过2-4当量的乙二胺进行切割，在该条件下，酯和糖肽是稳定的，并且不会发生氨基酸残基的消旋化。即使在同一分子内，未取代的邻苯二甲酰亚胺也不会在TCP切割过程中受到影响。TCP保护基充当供体上的β导向剂，在寡糖合成中的亲电偶联过程中也可以存在于受体物种上。
• Design and Synthesis of <i>C</i>₃-Symmetric Lewis^X Antigen
  作者：Yoshihiro Nishida、Tomoaki Tsurumi、Kenji Sasaki、Kenta Watanabe、Hirofumi Dohi、Kazukiyo Kobayashi

  DOI：10.1021/ol0351293

  日期：2003.10.1

  [GRAPHICS]C-3-Symmetric glycoconjugates carrying three equivalent Lewis(x) antigens or beta-lactosides were synthesized from p-nitrophenyl glycosides and trimesic acid via regio- and stereocontrolled glycosylation reactions. An H-1 NMR study has shown that the C-3-symmetric glycoconjugates soluble in water provide useful probes to investigate the Ca2+-dependent Lewis(x)-Lewis(x) association.
• ‘ClickCarb’: modular sugar based ligands via click chemistry
  作者：Noureddine Khiar、Raquel Navas、Inmaculada Fernández

  DOI：10.1016/j.tetlet.2011.11.043

  日期：2012.1

  Reported is a modular approach for the synthesis of a number of structurally diverse ligands derived from carbohydrates. The use of the highly functional hydroxy amino azide 1 derived from glucosamine allows the synthesis of a number of useful ligands for organic and organometallic catalyses. The key step of the approach is the Huisgen cycloaddition of the anomeric sugar azide and diverse alkynes. (C) 2011 Elsevier Ltd. All rights reserved.