12-tigloyl-14-hydroxy-17α-pregnane | 1304771-35-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: 12-tigloyl-14-hydroxy-17α-pregnane
• 英文别名: [(3S,8R,9S,10R,12R,13S,14S,17R)-17-acetyl-3,14-dihydroxy-10,13-dimethyl-1,2,3,4,7,8,9,11,12,15,16,17-dodecahydrocyclopenta[a]phenanthren-12-yl] (E)-2-methylbut-2-enoate
• CAS: 1304771-35-4
• 化学式: C₂₆H₃₈O₅
• 分子量: 430.585
• InChiKey: ATLKEQLPGRQWQA-JAHRXTSASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  83.8
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl-(1->4)-β-D-oleandropyranosyl-(1->4)-β-D-cymaropyranosyl-(1->4)-β-D-cymaropyranoside-12-β-tigloyl-14-β-hydroxy-17-β-pregnane 生成 12-tigloyl-14-hydroxy-17α-pregnane
  参考文献：
  名称：

  Pregnane steroidal glycosides and their cytostatic activities

  摘要：

  四种新的甾体苷，例如3-O-6-脱氧-3-O-甲基-β-d-别吡喃糖基-(1 → 4)-β-d-齐墩果吡喃糖基-(1 → 4)-β-d-吡喃吡喃糖基-(1 → 4)- β-d-吡喃酮苷-12-β-替格酰基-14-β-羟基-17-β-孕烷 (1)， 3-O-6-脱氧-3-O-甲基-β-d-别吡喃糖基-(1 → 4)-β-d-齐墩果吡喃糖基-(1 → 4)-β-d-吡喃吡喃糖基-(1 → 4)- β-d-cymaropyranoside-12-β-(2'-氨基)-苯甲酰基-14-β-羟基-17-β-孕烷(2), 3-O-6-脱氧-3-O-甲基-β-d-别吡喃糖基-(1 → 4)-β-d-齐墩果吡喃糖基-(1 → 4)-β-d-吡喃吡喃糖基-(1 → 4)-β-d-cymaropyranoside-12-β-14-β-二羟基-17-α-孕烷 (3) 和3-O-6-脱氧-3-O-甲基-β-d-别吡喃糖基-(1 → 4)-β-d-齐墩果吡喃糖基-(1 → 4)-β-d-吡喃吡喃糖基-(1 → 4)- β-d-cymaropyranoside-12-β-14-β-二羟基-17-β-pregnane (4) 是从Ceropegia fusca Bolle（萝藦科），一种景天科酸代谢植物，是加那利群岛的特有物种，在传统医学中用作疤痕剂、创伤剂和消毒剂。二氯甲烷提取物分别对 HL-60、A-431 和 SK-MEL-1 细胞、人白血病细胞、表皮样癌和黑色素瘤细胞表现出显着的细胞抑制活性。如表 I 所示，化合物 1 和 2 显示出非常相似的 IC50 值。 1 乙酰化得到二乙酸酯 5，对 HL-60 细胞的细胞毒性增加了 5 倍。化合物3和4在测定浓度下没有表现出细胞毒性。对于仅含有类固醇环 (6-8) 的化合物，带电荷的 O-氨基苯甲酰基而非替格酰基的存在提高了细胞毒性。

  DOI：

  10.1093/glycob/cwq203

文献信息

• Pregnane steroidal glycosides and their cytostatic activities
  作者：Víctor P García、Jaime Bermejo、Sara Rubio、José Quintana、Francisco Estévez

  DOI：10.1093/glycob/cwq203

  日期：2011.5

  Four new steroidal glycosides such as 3-O-6-deoxy-3-O-methyl-β-d-allopyranosyl-(1 → 4)-β-d-oleandropyranosyl-(1 → 4)-β-d-cymaropyranosyl-(1 → 4)-β-d-cymaropyranoside-12-β-tigloyl-14-β-hydroxy-17-β-pregnane (1), 3-O-6-deoxy-3-O-methyl-β-d-allopyranosyl-(1 → 4)-β-d-oleandropyranosyl-(1 → 4)-β-d-cymaropyranosyl-(1 → 4)-β-d-cymaropyranoside-12-β-(2'-amino)-benzoyl-14-β-hydroxy-17-β-pregnane (2), 3-O-6-deoxy-3-O-methyl-β-d-allopyranosyl-(1 → 4)-β-d-oleandropyranosyl-(1 → 4)-β-d-cymaropyranosyl-(1 → 4)-β-d-cymaropyranoside-12-β-14-β-dihydroxy-17-α-pregnane (3) and 3-O-6-deoxy-3-O-methyl-β-d-allopyranosyl-(1 → 4)-β-d-oleandropyranosyl-(1 → 4)-β-d-cymaropyranosyl-(1 → 4)-β-d-cymaropyranoside-12-β-14-β-dihydroxy-17-β-pregnane (4) were isolated from the aerial parts of Ceropegia fusca Bolle (Asclepiadaceae), a crassulacean acid metabolism plant, an endemic species to the Canary Islands that has been used in traditional medicine as a cicatrizant, vulnerary and disinfectant. The dichloromethane extract exhibited significant cytostatic activity against HL-60, A-431 and SK-MEL-1 cells, human leukemic, epidermoid carcinoma and melanoma cells, respectively. As shown in Table I, compounds 1 and 2 showed very similar IC50 values. The acetylation of 1 to give the diacetate 5 increases 5-fold the cytotoxicity against HL-60 cells. Compounds 3 and 4 did not show cytotoxicity at the assayed concentrations. With respect to the compounds containing only the steroid ring (6–8), the presence of a charged O-amino-benzoyl but not a tigloyl group improved the cytotoxicity.

  四种新的甾体苷，例如3-O-6-脱氧-3-O-甲基-β-d-别吡喃糖基-(1 → 4)-β-d-齐墩果吡喃糖基-(1 → 4)-β-d-吡喃吡喃糖基-(1 → 4)- β-d-吡喃酮苷-12-β-替格酰基-14-β-羟基-17-β-孕烷 (1)， 3-O-6-脱氧-3-O-甲基-β-d-别吡喃糖基-(1 → 4)-β-d-齐墩果吡喃糖基-(1 → 4)-β-d-吡喃吡喃糖基-(1 → 4)- β-d-cymaropyranoside-12-β-(2'-氨基)-苯甲酰基-14-β-羟基-17-β-孕烷(2), 3-O-6-脱氧-3-O-甲基-β-d-别吡喃糖基-(1 → 4)-β-d-齐墩果吡喃糖基-(1 → 4)-β-d-吡喃吡喃糖基-(1 → 4)-β-d-cymaropyranoside-12-β-14-β-二羟基-17-α-孕烷 (3) 和3-O-6-脱氧-3-O-甲基-β-d-别吡喃糖基-(1 → 4)-β-d-齐墩果吡喃糖基-(1 → 4)-β-d-吡喃吡喃糖基-(1 → 4)- β-d-cymaropyranoside-12-β-14-β-二羟基-17-β-pregnane (4) 是从Ceropegia fusca Bolle（萝藦科），一种景天科酸代谢植物，是加那利群岛的特有物种，在传统医学中用作疤痕剂、创伤剂和消毒剂。二氯甲烷提取物分别对 HL-60、A-431 和 SK-MEL-1 细胞、人白血病细胞、表皮样癌和黑色素瘤细胞表现出显着的细胞抑制活性。如表 I 所示，化合物 1 和 2 显示出非常相似的 IC50 值。 1 乙酰化得到二乙酸酯 5，对 HL-60 细胞的细胞毒性增加了 5 倍。化合物3和4在测定浓度下没有表现出细胞毒性。对于仅含有类固醇环 (6-8) 的化合物，带电荷的 O-氨基苯甲酰基而非替格酰基的存在提高了细胞毒性。
• Acid epimerization of 20-keto pregnane glycosides is determined by 2D-NMR spectroscopy
  作者：Víctor P. García

  DOI：10.1007/s10858-011-9499-z

  日期：2011.5

  Carbohydrates influence many essential biological events such as apoptosis, differentiation, tumor metastasis, cancer, neurobiology, immunology, development, host-pathogen interactions, diabetes, signal transduction, protein folding, and many other contexts. We now report on the structure determination of pregnane glycosides isolated from the aerial parts of Ceropegia fusca Bolle (Asclepiadaceae). The observation of cicatrizant, vulnerary and cytostatic activities in some humans and animals of Ceropegia fusca Bolle, a species endemic to the Canary Islands, encouraged us to begin a pharmacological study to determine their exact therapeutic properties. High resolution 1H-NMR spectra of pregnane glycosides very often display well-resolved signals that can be used as starting points in several selective NMR experiments to study scalar (J coupling), and dipolar (NOE) interactions. ROESY is especially suited for molecules such that ωτc ~ 1, where τc are the motional correlation times and ω is the angular frequency. In these cases the NOE is nearly zero, while the rotating-frame Overhauser effect spectroscopy (ROESY) is always positive and increases monotonically for increasing values of τc. The ROESY shows dipolar interactions cross peaks even in medium-sized molecules which are helpful in unambiguous assignment of all the interglycosidic linkages. Selective excitation was carried out using a double pulsed-field gradient spin-echo sequence (DPFGSE) in which 180° Gaussian pulses are sandwiched between sine shaped z-gradients. Scalar interactions were studied by homonuclear DPFGSE-COSY and DPFGSE-TOCSY experiments, while DPFGSE-ROESY was used to monitor the spatial environment of the selectively excited proton. Dipolar interactions between nuclei close in space can be detected by the 1D GROESY experiment, which is a one-dimensional counterpart of the 2D ROESY method. The C-12 and C-17 configurations were determined by ROESY experiments.

  碳水化合物影响许多重要的生物事件，如细胞凋亡、分化、肿瘤转移、癌症、神经生物学、免疫学、发育、宿主-病原体相互作用、糖尿病、信号转导、蛋白质折叠等。我们现在报告从毛花苣苔（Asclepiadaceae）的地上部分分离出的孕烷糖苷的结构测定。对毛花苣苔（一种加那利群岛特有的物种）在人和动物中的愈伤、创面愈合和细胞生长抑制活性的观察，促使我们开始进行药理学研究，以确定其确切的治疗特性。孕烷糖苷的高分辨率1H-NMR光谱通常显示清晰分辨的信号，这些信号可以用作一些选择性NMR实验的起点，以研究标量（J耦合）和偶极（NOE）相互作用。ROESY特别适用于ωτc ~ 1的分子，其中τc是运动相关时间，ω是角频率。在这种情况下，NOE几乎为零，而旋转框架Overhauser效应光谱（ROESY）总是正值，并且随着τc值的增加而单调增加。ROESY显示偶极相互作用交叉峰，即使在中型分子中也是如此，这有助于明确分配所有糖苷间连接。选择性激发使用双脉冲场梯度自旋回波序列（DPFGSE）进行，其中180°高斯脉冲