3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α,β-D-glucopyranosyl bromide | 189218-64-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α,β-D-glucopyranosyl bromide
• 英文别名: [(2R,3S,4R,5R)-3,4-diacetyloxy-6-bromo-5-(4,5,6,7-tetrachloro-1,3-dioxoisoindol-2-yl)oxan-2-yl]methyl acetate
• CAS: 189218-64-2
• 化学式: C₂₀H₁₆BrCl₄NO₉
• 分子量: 636.064
• InChiKey: IDKMVYIZIIGFMT-BZTFPRIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  35
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  126
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α,β-D-glucopyranosyl bromide 在 吡啶 、 盐酸 、 Ag Zeolite 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 69.0h， 生成 pent-4-enyl 3,4,6-tri-O-benzoyl-2-deoxy-2-tetrachlorophthalimido-β-D-glucopyranoside
  参考文献：
  名称：

  N-四氯邻苯二甲酰（TCP）用于氨基糖苷的保护/脱保护。

  摘要：

  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。

  DOI：

  10.1016/s0968-0896(96)00173-3
• 作为产物：
  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， 以 乙酸酐 为溶剂， 反应 27.0h， 生成 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α,β-D-glucopyranosyl bromide
  参考文献：
  名称：

  N-四氯邻苯二甲酰（TCP）用于氨基糖苷的保护/脱保护。

  摘要：

  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。

  DOI：

  10.1016/s0968-0896(96)00173-3

文献信息

• <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.
• Design, synthesis and biological evaluation of betulin-3-yl 2-amino-2-deoxy-β-d-glycopyranosides
  作者：Henryk Myszka、Daria Grzywacz、Magdalena Zdrowowicz、Paulina Spisz、Kamila Butowska、Janusz Rak、Jacek Piosik、Maciej Jaśkiewicz、Wojciech Kamysz、Beata Liberek

  DOI：10.1016/j.bioorg.2020.103568

  日期：2020.3

  Betulin is a natural pentacyclic triterpenoid, possessing a lupane-structure, with a wide range of pharmacological activities. Its weak hydrosolubility hinders the biological activity of the compound and its derivatives. To circumvent this problem, we synthesized and tested in vitro three d-glycosaminosides of betulin. The structure of betulin was modified by incorporation of 2-amino-2-deoxy-d-gluco-

  桦木蛋白是天然的五环三萜，具有卢潘结构，具有广泛的药理活性。它的弱水溶性阻碍了该化合物及其衍生物的生物学活性。为了解决这个问题，我们在体外合成并测试了三种甜菜碱的d-糖苷。通过将2-氨基-2-脱氧-d-葡萄糖-和-d-吡喃半乳糖苷基部分并入其C-3位来修饰桦木素的结构。迄今为止，文献中尚未报道含有这些氨基糖的白桦酰糖苷。通过1H和13C NMR光谱以及质谱证实了所研究衍生物的结构。28-O-乙酰基betulin-3-基2-氨基-2-脱氧-β-d-吡喃葡萄糖苷和betulin-3-基2-氨基-2-脱氧-β-d-葡萄糖和β-d-吡喃半乳糖苷是对人的致病真菌以及革兰氏阳性和革兰氏阴性细菌进行了测试。此外，在MCF-7乳腺癌细胞系和HDFa人皮肤成纤维细胞上进行了MTT细胞毒性试验。诱变特性的Ames测试完成了我们的生物学测定。
• Synthesis and induction of apoptosis in B cell chronic leukemia by diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside hydrochloride and its derivatives
  作者：Henryk Myszka、Dorota Bednarczyk、Maria Najder、Wiesław Kaca

  DOI：10.1016/s0008-6215(02)00407-x

  日期：2003.1

  2-Acetamido-2-deoxy-D-glucose hydrochloride (D-glucosamine hydrochloride) has been used for the preparation of 1,3.4.6-tetra- O-acetyl-2-deoxy-2-trifluoroacetqamido-beta- (4) and 2-tetrachlorophthalimido-alpha, beta-D-glucopyranose (6) which have been transformed into the appropriate bromides and the chloride. Both bromo and chloro sugars were used as a glycosyl donors for the glycosylation of diosgenin [(25R)-spirost-5-en-3beta-ol]. These condensations were conducted under mild conditions, using silver triflate as a promoter, and gave diosgenyl glycosides 9 and 12. Each of them was converted into diosgenyl 2-amino-2-deoxy-beta-D-glucopyranoside hydrochloride (11) and N-acylamido derivatives. The structures of all new glycosides were established by H-1 and C-13 NMR spectroscopy. These diosgenyl glycosides are the first saponins containing the D-glucosamine residue that have been synthesized. These compounds show promising antitumor activities, The synthetic saponins increase the number of apoptotic B cells, in combination with cladribine (2-CdA). that are isolated from chronic lymphotic leukemia (B-CLL) patients. (C) 2002 Published by Elsevier Science Lid.
• The synthesis of diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside hydrochloride
  作者：Dorota Bednarczyk、Wiesław Kaca、Henryk Myszka、Lilianna Serwecińska、Zygfryd Smiatacz、Andrzej Zaborowski

  DOI：10.1016/s0008-6215(00)00199-3

  日期：2000.9

  The N-trifluoroacetyl- and N-tetrachlorophthaloyl-protected bromide of D-glucosamine has been used for the first time as a glycosyl donor for the glycosylation of diosgenin [(25R)-spirost-5-en-3 beta-ol]. Both 1,3,4,6-tetra-O-acetyl-2-deoxy-2-trifluoroacetamido-beta-D-glucopyranoside and 1,3,4,6-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-alpha,beta-D-glucopyranoside were transformed into the appropriate glycosyl bromides. These reacted with diosgenin under mild conditions, using silver triflate as a promoter, and gave the corresponding protected diosgenyl glycosides. Each was deprotected to give diosgenyl 2-amino-2-deoxy-beta-D-glucopyranoside hydrochloride. The structures of the new glycosides were established by H-1 NMR spectroscopy. (C) 2000 Elsevier Science Ltd. All rights reserved.