2,3,4-tri-O-benzoyl-β-L-arabinopyranosyl trichloroacetimidate-⁴C₁ | 247017-34-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4-tri-O-benzoyl-β-L-arabinopyranosyl trichloroacetimidate-⁴C₁
• 英文别名: 2,3,4-tri-O-benzoyl-β-L-arabinopyranosyl trichloroacetimidate；perbenzoylated arabinosyl trichloroacetimidate；perbenzoylated arabinose trichloroacetimidate；[(3S,4S,5R,6R)-4,5-dibenzoyloxy-6-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl] benzoate
• CAS: 247017-34-1
• 化学式: C₂₈H₂₂Cl₃NO₈
• 分子量: 606.844
• InChiKey: CTJJXLYHZINRRA-BTKWVRSESA-N

物化性质

• 沸点：
  651.9±65.0 °C(Predicted)
• 密度：
  1.43±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  40
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  121
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2,3,4-tri-O-benzoyl-β-L-arabinopyranosyl trichloroacetimidate-⁴C₁ 在 4 A molecular sieve 、 三氟化硼乙醚 、 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 10.0h， 生成 (2S,3R,4E)-2',3',4'-tri-O-benzoyl-α-L-arabinopyranosyl-(1'->1)-2-(hexadecanoylamido)-3-O-benzoyl-4-octadecene-1,3-diol
  参考文献：
  名称：

  Efficient Syntheses of a Series of Glycosphingolipids with 1,2‐trans‐Glycosidic Linkages

  摘要：

  A series of glycosphingolipids with 1,2-trans-glycosidic linkages were synthesized in the presence of neighboring group participation using trichloroacetimidates as glycosyl donors and an azido-sphingosine as the glycosyl acceptor. During the preparation of the target compounds, it was found that the alpha-L-arabinopyranosyl unit in target 7e and intermediates 7b - 7d existed in the C-1(4) conformation and that the b-L-fucopyranosyl unit in 10e adopted the C-4(1) conformation.

  DOI：

  10.1080/07328300600859825
• 作为产物：
  描述：

  L-(+)-arabinose 在 吡啶 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 甲胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 2,3,4-tri-O-benzoyl-β-L-arabinopyranosyl trichloroacetimidate-⁴C₁
  参考文献：
  名称：

  四种蛇毒皂苷元糖苷作为α-葡萄糖苷酶抑制剂的合成与评价

  摘要：

  四个常春配基糖苷1 - 4通过与单糖单罐顺序的糖基化进行有效地合成1-（三氯乙酰亚胺酯）S作为供体，导致显著简化合成方法没有糖基化的中间体的隔离。合成常春配基糖苷的活性1 - 4针对α葡糖苷酶IV型进行评价; 常春配基糖苷4含有α -大号-rhamnopyranosyl单元显示出最好的活性，其IC 50为47.9μ值中号。

  DOI：

  10.1002/hlca.201200128

文献信息

• Synthesis ofα-Hederin,δ-Hederin, and Related Triterpenoid Saponins
  作者：Karen Plé、Martin Chwalek、Laurence Voutquenne-Nazabadioko

  DOI：10.1002/ejoc.200300723

  日期：2004.4

  osyl]hederagenin, 1), δ-hederin (3-O-(α-L-arabinopyranosyl)hederagenin, 3), and three related triterpenoid saponins is described as part of a study of the structure−activity relationships between triterpenoid saponins and hemolytic activity. 4-Methoxybenzyl α-L-arabinopyranoside (11) was synthesized first and then used to prepare the different arabinose acceptors. Glycosylation between the acceptors

  α-hederin (3-O-[α-L-rhamnopyranosyl-(1⇄2)-α-L-arabinopyranosyl]hederagenin, 1), δ-hederin (3-O-(α-L-arabinopyranosyl)的合成hederagenin, 3) 和三种相关的三萜皂苷被描述为三萜皂苷与溶血活性之间构效关系研究的一部分。首先合成 4-甲氧基苄基 α-L-阿拉伯吡喃糖苷 (11)，然后用于制备不同的阿拉伯糖受体。受体和 2,3,4-三-O-苯甲酰基-α-L-吡喃鼠李糖基三氯乙酰亚胺酯 (20) 之间的糖基化以极好的收率进行，得到所需的二糖。二糖的三氯乙酰亚胺衍生物与烯丙基-或甲基常春藤苷配伍以高产率得到受保护的皂苷。然后在脱保护后以良好至中等的产率获得皂苷及其相应的甲酯。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
• Synthesis of furostanol glycosides: discovery of a potent α-glucosidase inhibitor
  作者：Peng Wang、Jiejie Hao、Xiuli Zhang、Cong Wang、Huashi Guan、Ming Li

  DOI：10.1039/c6ob01766e

  日期：——

  A convenient approach to the synthesis of furostanol glycosides has been developed with the features of both highly efficient incorporation of a 26-O-β-D-glucopyranosyl unit and ready formation of hemiketal ring E. The total syntheses of seven furostanol saponins including funlioside B, lilioglycoside, protobioside I, protodioscin, pallidifloside I, coreajaponins A and parisaponin I are efficiently

  已经开发了一种方便的合成糠醛甾醇糖苷的方法，该方法具有高效掺入26- O- β- D-吡喃葡萄糖基单元和易于形成半缩酮环E的特点。七种糠醛甾醇皂苷的总合成包括fun素B使用容易获得的16β-乙酰氧基-22-氧代-26-羟基胆甾醇衍生物作为有效的构建基块可有效地获得，，，，，、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、还评估了合成皂苷的α-葡萄糖苷酶抑制活性，这表明fun药苷B是开发α-葡萄糖苷酶抑制剂的高度潜在的先导。
• [EN] BIDESMOSIDIC BETULIN AND BETULINIC ACID DERIVATIVES AND USES THEREOF AS ANTITUMOR AGENTS<br/>[FR] DÉRIVÉS DE BÉTULINE BIDESMOSIDIQUE ET D'ACIDE BÉTULINIQUE, ET LEURS UTILISATIONS EN TANT QU'AGENTS ANTICANCÉREUX
  申请人：UNIV QUEBEC A CHICOUTIMI

  公开号：WO2010028487A1

  公开（公告）日：2010-03-18

  The instant application is directed to bidesmosidic betulin and betulinic acid saponin derivatives of formula (I), and use thereof as antitumor agents. In particular, said compounds are effective in treating lung carcinomas, colorectal adenocarcinomas, breast adenocarcinomas, and prostate adenocarcinomas. Methods of synthesizing said compounds through selective glycosylation of the C-28 and C-3 position, and diagnostic methods for identifying tumours suitable for treatment by said compounds are also disclosed.

  该即时申请涉及到公式(I)的双萜基萜苷类的白桦酸和白桦酸皂苷衍生物，以及其作为抗肿瘤剂的用途。具体来说，所述化合物在治疗肺癌、结肠腺癌、乳腺腺癌和前列腺腺癌方面具有有效性。还公开了通过选择性糖基化C-28和C-3位置合成所述化合物的方法，以及用于识别适合通过所述化合物治疗的肿瘤的诊断方法。
• Synthesis of novel diosgenyl saponin analogues and apoptosis-inducing activity on A549 human lung adenocarcinoma
  作者：Bo Wang、Jaemoo Chun、Yang Liu、Lina Han、Yan-shi Wang、Eun-Ji Joo、Yeong-Shik Kim、Mao-sheng Cheng

  DOI：10.1039/c2ob26579f

  日期：——

  We synthesized a diosgenyl saponin bearing a unique disaccharide from the natural product β-hederin, together with twelve glycosylated derivatives and determined their cytotoxicity against five different human cancer cell lines. Most of them showed weak cytotoxicity, with the exception of compound 20, diosgenyl α-L-rhamnopyranosyl-(1→2)-[α-L-arabinopyranosyl-(1→4)]-α-L-arabinopyranoside, which exhibited strong cytotoxicity against A549 cells. The cytotoxicity of 20 was associated with apoptotic cell death, which was characterized by morphological changes, chromatin condensation, DNA fragmentation, and phosphatidylserine externalization. Compound 20 induced apoptosis of A549 cells through a caspase-8-mediated extrinsic pathway and a caspase-9-mediated intrinsic pathway. In addition, phosphorylation of JNK increased but the phosphorylation of ERK decreased after treatment with 20. These results provide a basic mechanism for the anticancer activity of 20.

  我们合成了一种独特的含有二糖结构的地奥配基皂苷，源自天然产物β-常春藤素，并制备了十二种糖基化衍生物，测定了它们对五种不同的人类癌细胞系的细胞毒性。大多数衍生物显示出较弱的细胞毒性，例外的是化合物20，即地奥配基α-L-鼠李糖吡喃糖基-(1→2)-[α-L-阿拉伯糖吡喃糖基-(1→4)]-α-L-阿拉伯糖吡喃糖苷，对A549细胞表现出强烈的细胞毒性。化合物20的细胞毒性与其诱导的细胞凋亡有关，其特征包括形态学改变、染色质凝集、DNA断裂和磷脂酰丝氨酸外翻。化合物20通过caspase-8介导的外源途径和caspase-9介导的内源途径诱导A549细胞凋亡。此外，经化合物20处理后，JNK的磷酸化水平升高，而ERK的磷酸化水平降低。这些结果为化合物20的抗癌活性提供了基本机制。
• Facile Synthesis of the Naturally Cytotoxic Triterpenoid Saponin Patrinia-Glycoside B-II and Its Conformer
  作者：Li Ren、Yong-Xiang Liu、Dan Lv、Mao-Cai Yan、Han Nie、Yang Liu、Mao-Sheng Cheng

  DOI：10.3390/molecules181215193

  日期：——

  The first chemical synthesis of the natural triterpenoid saponin Patrinia-glycoside B-II, namely oleanolic acid 3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-gluco-pyranosyl-(1→3)]-α-L-arabinopyranoside, has been accomplished in a linear 11-step sequence 11 with 9.4% overall yield. The abnormal 1C4 conformation of the arabinose residue was found to occur via conformational fluctuation during preparation of the intermediates. Molecular mechanism and quantum chemistry calculations showed that Patrinia-glycoside B-II and its conformer 1 cannot interconvert under normal conditions. Preliminary structure-activity relationships studies indicated that the 4C1 chair conformation of the arabinose residue in the unique α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranosyl disaccharide moiety is one of the chief positive factors responsible for its cytotoxic activity against tumors.

  首次以线性 11 步序列 11 完成了天然三萜皂苷 Patrinia-glycoside B-II 即齐墩果酸 3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-Gluco-pyranosyl-(1→3)]-α-L-arabinopyranoside 的化学合成，总收率为 9.4%。研究发现，阿拉伯糖残基的异常 1C4 构象是在制备中间体的过程中通过构象波动产生的。分子机理和量子化学计算表明，在正常条件下，帕特里尼亚糖苷 B-II 及其构象 1 不能相互转化。初步的结构-活性关系研究表明，独特的α-L-吡喃鼠李糖基-(1→2)-α-L-阿拉伯吡喃糖基二糖分子中阿拉伯糖残基的 4C1 椅构象是其对肿瘤具有细胞毒性活性的主要积极因素之一。