benzyl 3-O-(2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl-(1->2)-α-L-arabinopyranosyl)-oleanolate | 875878-36-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: benzyl 3-O-(2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl-(1->2)-α-L-arabinopyranosyl)-oleanolate
• 英文别名: benzyl oleanolate 3-O-2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl-(1->2)-α-L-arabinopyranoside；benzyl oleanolate 3-O-2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside；benzyl (4aS,6aR,6aS,6bR,8aR,10S,12aR,14bS)-10-[(2S,3R,4S,5S)-4,5-dihydroxy-3-[(2S,3R,4R,5S,6S)-3,4,5-tribenzoyloxy-6-methyloxan-2-yl]oxyoxan-2-yl]oxy-2,2,6a,6b,9,9,12a-heptamethyl-1,3,4,5,6,6a,7,8,8a,10,11,12,13,14b-tetradecahydropicene-4a-carboxylate
• CAS: 875878-36-7
• 化学式: C₆₉H₈₄O₁₄
• 分子量: 1137.42
• InChiKey: OBROSHOFEBVEKF-UDXNNPIPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.4
• 重原子数：
  83
• 可旋转键数：
  17
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  183
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  benzyl 3-O-(2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl-(1->2)-α-L-arabinopyranosyl)-oleanolate 在 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.0h， 以57%的产率得到
  参考文献：
  名称：

  EP3973965

  摘要：

  公开号：
• 作为产物：
  描述：

  benzyl oleanolate 3-O-2,3,4-tri-O-benzoyl-α-L-arabinopyranoside 在 4 A molecular sieve 、 三氟化硼乙醚 、 sodium methylate 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 4.0h， 生成 benzyl 3-O-(2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl-(1->2)-α-L-arabinopyranosyl)-oleanolate
  参考文献：
  名称：

  Synthesis of β-hederin and Hederacolchiside A1: triterpenoid saponins bearing a unique cytotoxicity-inducing disaccharide moiety

  摘要：

  A facile synthetic approach toward oleanolic acid glycoside bearing alpha-L-rhamnopyranosyl-(1 -> 2)-alpha-L-arabinopyranosyl moiety, a unique oligosaccharide that strongly induces antitumor activity of oleanane-type triterpenoid saponins, was developed. Based on this approach P-hederin (oleanolic acid 3-0-Gt-L-rhamnopyranosyl-(1 -> 2)-alpha- L-arabinopyrano side) was efficiently prepared from oleanolic acid through stepwise glycosylation in linear eight steps with 52% overall yield, while Hederacolchiside A, (oleanolic acid 3-O-alpha-L-rhamnopyranosyl-(1 -> 2)-[beta-D-glucopyranosyl-(1 -> 4)]-alpha-L-arabinopyranoside) in linear 13 steps with 20% overall yield. (c) 2005 Published by Elsevier Ltd.

  DOI：

  10.1016/j.carres.2005.10.015

文献信息

• 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。
• Synthesis and Tumor Cytotoxicity of Novel Amide Derivatives of β-Hederin
  作者：Yang Liu、Wen-Xiang Lu、Mao-Cai Yan、Yang Yu、Takashi Ikejima、Mao-Sheng Cheng

  DOI：10.3390/molecules15117871

  日期：——

  Thirteen novel triterpenoid saponins, designed as amide derivatives of the natural cytotoxic saponin β-hederin, were synthesized by a stepwise glycosylation strategy. The in vitro cytotoxic activity of these compounds was evaluated against five different tumor cell lines. Most of the evaluated compounds showed effective inhibitory activity against at least one tumor cell line at micromolar concentrations. The preliminary structure-activity relationships (SAR) indicate that mide derivatization at C-28 resulted in highly cytotoxic derivatives on specific tumor cell lines, and also resulted in an increase in the antitumor selectivity of β-hederin.

  通过逐步糖基化策略合成了 13 种新型三萜皂苷，设计为天然细胞毒性皂苷 β-常春藤素的酰胺衍生物。针对五种不同的肿瘤细胞系评估了这些化合物的体外细胞毒活性。大多数评估的化合物在微摩尔浓度下对至少一种肿瘤细胞系表现出有效的抑制活性。初步的构效关系（SAR）表明，C-28位点的mide衍生化产生了对特定肿瘤细胞系具有高度细胞毒性的衍生物，并且还导致β-常春藤素的抗肿瘤选择性增加。
• Facile synthesis and cytotoxicity of triterpenoid saponins bearing a unique disaccharide moiety: hederacolchiside A1 and its analogues
  作者：Mao-Cai Yan、Yang Liu、Wen-Xiang Lu、Hui Wang、Yu Sha、Mao-Sheng Cheng

  DOI：10.1016/j.carres.2007.12.014

  日期：2008.3

  An improved synthetic approach toward hederacolchiside A(1), an antitumor triterpenoid saponin bearing a unique disaccharide moiety, was established. This approach began from a partially protected intermediate and avoided tedious protection-deprotection manipulation. An abnormal ring conformation ((1)C(4)) of the center arabinose residue was found in the intermediate, which may account for the unusual regioselectivity between 3-OH and 4-OH of arabinose. Two analogues of hederacolchiside A(1) were then facilely prepared by this approach and exhibited significant cytotoxicity in preliminary in vitro assay. (c) 2007 Elsevier Ltd. All rights reserved.