(23R,25R)-3β-acetoxy-16α,23:23,26-diepoxy-5α-cholestan-22-one | 140195-62-6

• 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: (23R,25R)-3β-acetoxy-16α,23:23,26-diepoxy-5α-cholestan-22-one
• 英文别名: (23R,25R)-3β-acetoxy-16β,23:23,26-diepoxy-5α-cholestan-22-one；[(1R,2S,4S,4'R,6R,8S,9R,10S,13S,14S,17S,19S)-4',8,10,14-tetramethyl-7-oxospiro[5-oxapentacyclo[11.8.0.02,10.04,9.014,19]henicosane-6,2'-oxolane]-17-yl] acetate
• CAS: 140195-62-6
• 化学式: C₂₉H₄₄O₅
• 分子量: 472.665
• InChiKey: YCSUZCGVZXOVDX-QCARREOOSA-N

物化性质

• 沸点：
  557.5±40.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (23R,25R)-3β-acetoxy-16α,23:23,26-diepoxy-5α-cholestan-22-one 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以74%的产率得到(23Z,25R)-3β,26-diacetoxy-16β,23-epoxy-5α-cholest-23-ene-22-one
  参考文献：
  名称：

  Regio- and stereoselective cleavage of steroidal 22-oxo-23-spiroketals catalyzed by BF3·Et2O

  摘要：

  The regioselective opening of the F ring of 22-oxo-23-spiroketals using BF3 center dot OEt2 in acetic anhydride yielded novel cholestanic frameworks with pyranone E ring 20-23. The structures of the new derivatives of botogenin, diosgenin, hecogenin and tigogenin thus obtained were established using one and two dimensional H-1, C-13 experiments (DEPT, COSY, HETCOR, HMBC). The X-ray diffraction analysis unequivocally confirmed the R configuration at C-23 in the starting 22-oxo-23-spiroketal 18 and the Z configuration of the C-23-C-24 double bond in the reaction product 20. (C) 2015 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2015.04.004
• 作为产物：
  描述：

  23-oxotigogenin acetate 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以99%的产率得到(23R,25R)-3β-acetoxy-16α,23:23,26-diepoxy-5α-cholestan-22-one
  参考文献：
  名称：

  路易斯酸介导的C-22螺缩醛（25 R）-3β-乙酰氧基-5α-spirostan-23-one的异构化：一种合成C-23螺缩醛类固醇皂苷元的方法

  摘要：

  用四氯化钛处理（25 R）-3β-乙酰氧基-5α-螺氧杂环丁烷-23-一（23-氧代-蛇毒苷原乙酸酯）3，以优异的收率得到22-氧代-23-螺缩醛异构体4。

  DOI：

  10.1039/c39920000275

文献信息

• On reactions of spirostane sapogenins with benzeneseleninic anhydride
  作者：Izabella Jastrzębska、Aneta Dobrogowska、Ewa Lutostańska、Jacek W. Morzycki

  DOI：10.1016/j.tet.2010.05.013

  日期：2010.7

  Direct dehydrogenation of spirostane sapogenins with benzeneseleninic anhydride/iodoxybenzene afforded the Δ22 derivatives in low yields. The reactions catalyzed by BF3/Et2O produced the 23-oxo-sapogenins in addition to their 22-oxo-23-spiro-isomers. The reactions of sapogenins with benzeneseleninic anhydride carried out in the presence of TiCl4 afforded products chlorinated at C23.

  与spirostane皂角苷配基的直接脱氢苯亚硒酸酐/ iodoxybenzene得到Δ 22在低的产率的衍生物。BF 3 / Et 2 O催化的反应除了生成22-oxo-23-spiro异构体外，还生成了23-oxo-sapogenins。皂苷元与苯硒二酸酐的反应在TiCl 4的存在下进行，得到在C23氯化的产物。
• TiCl4 catalyzed cleavage of (25R)-22-oxo-23-spiroketals. Synthesis of sapogenins with furostanol and pyranone E rings on the side chain
  作者：Alejandro Corona-Díaz、J. Pablo García-Merinos、María E. Ochoa、Rosa E. del Río、Rosa Santillan、Susana Rojas-Lima、Jacek W. Morzycki、Yliana López

  DOI：10.1016/j.steroids.2019.108488

  日期：2019.12

  The regioselective opening of the F ring of 22-oxo-23-spiroketals 7a-d using TiCl4 in acetic anhydride yielded the novel furostanols 11a-d along with cholestanic derivatives 8a-d with pyranone E ring. The structures of the new derivatives thus obtained were established using one- (DEPT) and two-dimensional 1H, 13C NMR experiments (COSY, HSQC, HMBC, NOESY). The 22α-hydroxyl orientation in compounds

  在乙酸酐中使用 TiCl4 对 22-oxo-23-spiroketals 7a-d 的 F 环进行区域选择性打开，产生了新型呋喃烷醇 11a-d 以及带有吡喃酮 E 环的胆甾烷衍生物 8a-d。使用一维(DEPT)和二维1H、13C NMR实验(COSY、HSQC、HMBC、NOESY)建立由此获得的新衍生物的结构。化合物 11a-d 中的 22α-羟基取向是通过将 13C 化学位移与该家族其他苷元成员的化学位移进行比较而提出的，并通过化合物 11a 的 NOESY 和 X 射线衍射分析证实。
• The synthesis and antifungal activity of (20 S )-3β-acetoxy-5α-pregnane-20,16β-carbolactone against fluconazole – Resistant Candida cells
  作者：Izabella Jastrzebska、Katarzyna Niemirowicz、Wioleta I. Brzozowska、Robert Bucki

  DOI：10.1016/j.steroids.2016.12.009

  日期：2017.2

  An efficient procedure for the synthesis of (20S)-3 beta-acetoxy-511-pregnane-20,16 beta-carbolactone is described. Bactericidal and fungicidal activity of the lactone against different bacteria such as MSSA, MESA, E. coli ESBL, P. aeruginosa and clinical isolates of Candida spp., in planktonic and biofilm growth stage were assessed. Additionally, the affinity of this new compound to microbial plasma membrane and hemoglobin release from human red blood cells were determined using fluorometric arid colorimetric assay, respectively. Our studies revealed that the lactone exhibits strong antifungal activity, and the ability to prevent pathogens' biofilm formation. Additionally, upon lactone treatment a significant affinity to fungal, but not to human cell membranes, indicating suitable biocompatibility was observed. (C) 2016 Elsevier Inc. All rights reserved.
• On reactions of steroidal 23-oxo and 23,24-epoxysapogenins with Lewis acids
  作者：Izabella Jastrzębska、Leszek Siergiejczyk、Aneta M. Tomkiel、Zofia Urbańczyk-Lipkowska、Dominik Wójcik、Jacek W. Morzycki

  DOI：10.1016/j.steroids.2009.02.010

  日期：2009.8

  The reaction of 23-oxotigogenin acetate with TMSOTf in THF afforded the corresponding bisnorcholanic lactone in 60% yield. The analogous reactions carried out in dichloromethane or benzene gave the rearranged products-the isometric spirostanic ketone (10-15%) and bisfuran (40-42%). Similar products were also obtained upon treatment of 23,24-epoxysapogenins with BF3. The epoxides treated with TiCl4 afforded mostly chlorohydrins and no rearranged products were detected. (C) 2009 Elsevier Inc. All rights reserved.