26-thiodiosgenin | 55028-76-7

• 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: 26-thiodiosgenin
• 英文别名: (1S,2S,4S,5'R,6S,7S,8R,9S,12S,13R,16S)-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icos-18-ene-6,2'-thiane]-16-ol
• CAS: 55028-76-7
• 化学式: C₂₇H₄₂O₂S
• 分子量: 430.695
• InChiKey: SCHFOYLFANARFN-MEPOCMDBSA-N

物化性质

• 沸点：
  556.3±50.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  30
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  54.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  26-thiodiosgenin 在 咪唑 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  薯蓣皂苷元 26-硫类似物的化学和生物活性研究：26-硫薯皂苷元 S-单氧化物和二氧化物及其烷基衍生物的合成。

  摘要：

  详细阐述了 MCPBA 将 26-硫薯蓣皂苷元氧化为相应的亚砜和砜的化学选择性程序。观察到溶液中亚砜的异常平衡。此外，研究了亚砜和砜的α-烷基化。最后，检测了所得化合物的生物活性。

  DOI：

  10.3390/molecules28010189
• 作为产物：
  描述：

  (3b,25R)-3-hydroxyfurosta-5,20(22)-dien-26-yl 4-Methylbenzenesulfonate 在 potassium hydroxide 作用下， 以 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 27.75h， 生成 26-thiodiosgenin
  参考文献：
  名称：

  Convergent synthesis and cytotoxic activities of 26-thio- and selenodioscin

  摘要：

  Convergent block syntheses of 26-thio- and selenodioscin have been achieved by developing the highly stereoselective 1,2-trans glycosylations of chacotriosyl imidate without recourse to neighboring group assistance. Both thiodioscin and selenodioscin possess cytotoxic activities similar to dioscin, a natural spirostanol glycoside. (C) 2013 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2013.05.018

文献信息

• Preparations of heterospirostanols and their pharmacological activities
  作者：Hang-Ji Quan、Jyunichi Koyanagi、Koichi Ohmori、Shinichi Uesato、Tetsuaki Tsuchido、Setsuo Saito

  DOI：10.1016/s0223-5234(02)01386-7

  日期：2002.8

  (3beta,20S,22S,25R)-22-Thiospirosol-5-en-3-ol (9) and (3beta,20S,22S,25R)-22-seleno-spirosol-5-en-3-ol (11) were prepared from diosgenin (3) via 26-iodopseudodiosgenin (6) as a key intermediate. Diosgenone (15), solasodinone (16), (20S,22S,25R)-22-thiospirosol-4-en-3-one (17), (20 S,22S,2 5R)-22-selenospirosol-4-en-3-one (18) and (20R,22S, 2 5R)-spirosol-4-en-3-one (19) were prepared by Oppenauer oxidation of 3, solasodine 4, 9, 11 and (3beta,20R,22R,25R)-spirosol-5-en-3-ol 14, respectively. Oxidations of 15 and 16 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) provided corresponding dienone products, (20S,22S,25R)spirosol-1,4-dien-3 -one (20) and (20S, 22S, 25R)-22-thiospirosol-1,4-dien-3 -one (21), respectively, while oxidation of 19 (C-20 diastereoisomer of 15) gave no dienone product but 21-exo vinyl product 22. 26-Thioacetylpseudodiosgenone (24) and 26-cyanoselenopseudodiosgenone (25) were prepared by treatment of 26-iodopseudodiosgenose (23), which was obtained by Oppenauer oxidation of 6, with potassium thioacetate and potassium selenocyanate, respectively. Compounds 15 and 19 exhibited more than 80% inhibitions in INF-gamma productions at 10.0 muM. Compounds 4 and 25 showed cytotoxic activities (IC50 = 6 and 5 muM, respectively) against cancerous HCT 116 cell lines. Compounds 12 and 25 had antiurease activities (IC50 = 12.4 and 11.4 muM, respectively), in which only the latter showed an inhibition zone (mean zone diameter = 12.2 mm) formed by Bacillus subtilis 168 trp. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

  (3β,20S,22S,25R)-22-硫二环甾-5-烯-3-醇 (9) 和 (3β,20S,22S,25R)-22-硒二环甾-5-烯-3-醇 (11) 通过以 26-碘伪 Diosgenin (6) 为关键中间体，从 Diosgenin (3) 中制备得到。Diosgenone (15)、Solasodinone (16)、(20S,22S,25R)-22-硫二环甾-4-烯-3-酮 (17)、(20S,22S,25R)-22-硒二环甾-4-烯-3-酮 (18) 和 (20R,22S,25R)-二环甾-4-烯-3-酮 (19) 分别由 Oppenauer 氧化 Diosgenin (3)、Solasodine (4)、9、11 和 (3β,20R,22R,25R)-二环甾-5-烯-3-醇 (14) 制得。15 和 16 与 2,3-二氯-5,6-二氰基-1,4-苯并醌 (DDQ) 的氧化反应分别生成相应的二烯酮产物：(20S,22S,25R)-二环甾-1,4-二烯-3-酮 (20) 和 (20S,22S,25R)-22-硫二环甾-1,4-二烯-3-酮 (21)。然而，19 (15 的 C-20 对映异构体) 的氧化未产生二烯酮产物，而是生成了外侧烯烃产物 22。26-硫代乙酰基伪 Diosgenone (24) 和 26-亚硝基硒代伪 Diosgenone (25) 通过分别用硫代乙酸钾和硒代亚硝酸钾处理由 6 的 Oppenauer 氧化产物 23 制得。化合物 15 和 19 在 10.0 μM 浓度下对 INF-γ 的生产表现出超过 80% 的抑制作用。化合物 4 和 25 对癌细胞 HCT 116 系显示出细胞毒性活性 (IC50 = 6 和 5 μM)。化合物 12 和 25 具有抗尿酶活性 (IC50 = 12.4 和 11.4 μM)，其中只有后者表现出由 Bacillus subtilis 168 trp 形成的抑制区 (平均区直径 = 12.2 mm)。 © 2002 Editions scientifiques et médicales Elsevier SAS. 保留所有权利。
• Synthesis and cytotoxic effect of pseudodiosgenyl saponins with thio-ring F
  作者：Xin Zan、Jian Gao、Guofeng Gu、Shanshan Liu、Bin Sun、Lei Liu、Hong-Xiang Lou

  DOI：10.1016/j.bmcl.2014.01.055

  日期：2014.3

  Both the sugar moieties and aglycons of steroid saponins play important roles for their bioactivities. In order to test the biological contribution of the glycosyl residue and search new saponins with notable anticancer activity, mono- and di-saccharide pseudodiosgenyl saponins 22-28 together with two pseudodiosgenyl conjugates 29 and 30 were conveniently synthesized, all of which were based on the aglycon 7 bearing the thio-ring F. The cytotoxicity on human cancer cells (MCF-7, HepG-2, A549) for all of the synthesized compounds 7 and 22-30 was evaluated by MTT method. The thio-aglycon 7 when conjugated with sugars exhibited potent cytotoxicity, and the introduction of D-glucosamine into aglycon 7 led to the most potent compound 28. Furthermore, DAPI staining, AV/PI staining, AO-relocation, AO-uptake and LysoTracker Red-uptake assays demonstrated that the cell death caused by neosaponin 28 was at least partially through apoptosis involving lysosomal membrane permeabilization. (C) 2014 Elsevier Ltd. All rights reserved.
• Solasodine-3- O -β- d -glucopyranoside kills Candida albicans by disrupting the intracellular vacuole
  作者：Wenqiang Chang、Ying Li、Ming Zhang、Sha Zheng、Yan Li、Hongxiang Lou

  DOI：10.1016/j.fct.2017.05.045

  日期：2017.8

  The increasing incidence of fungal infections and emergence of drug resistance underlie the constant search for new antifungal agents and exploration of their modes of action. The present study aimed to investigate the antifungal mechanisms of solasodine-3-O-beta-D-glucopyranoside (SG) isolated from the medicinal plant Solanum nigrum L. In vitro, SG displayed potent fungicidal activity against both azole-sensitive and azole-resistant Candida albicans strains in Spider medium with its MICs of 32 mu g/ml Analysis of structure and bioactivity revealed that both the glucosyl residue and NH group were required for SG activity. Quantum dot (QD) assays demonstrated that the glucosyl moiety was critical for SG uptake into Candida cells, as further confirmed by glucose rescue experiments. Measurement of the fluorescence intensity of 2',7'-dichlorofluorescin diacetate (DCFHDA) by flow cytometry indicated that SG even at 64 mu g/ml just caused a moderate increase of reactive oxygen species (ROS) generation by 58% in C. albicans cells. Observation of vacuole staining by confocal microscopy demonstrated that SG alkalized the intracellular vacuole of C. albicans and caused hyper-permeability of the vacuole membrane, resulting in cell death. These results support the potential application of SG in fighting fungal infections and reveal a novel fungicidal mechanism. (C) 2017 Published by Elsevier Ltd.