3β-acetoxy-12β-hydroxy-5α,25R-spirostan | 863-85-4

• 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: 3β-acetoxy-12β-hydroxy-5α,25R-spirostan
• 英文别名: 12β-hydroxytigogenin；(25R)-3β-Acetoxy-5α-spirostan-12β-ol
• CAS: 863-85-4
• 化学式: C₂₉H₄₆O₅
• 分子量: 474.681
• InChiKey: MUKOGWNBXRLZHQ-HBHRVFMHSA-N

物化性质

• 熔点：
  211-213 °C(Solv: methanol (67-56-1))
• 沸点：
  559.3±50.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.34
• 重原子数：
  34.0
• 可旋转键数：
  1.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.97
• 拓扑面积：
  64.99
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  3β-acetoxy-12β-hydroxy-5α,25R-spirostan 在 铂 甲基环氧丙烷 、 高氯酸 、 氧气 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 、 乙酸乙酯 、 丙酮 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 39.0h， 生成 [(1R,2S,4S,5'R,6R,7S,8R,9S,10R,12S,13S,15R,17R,19S)-17-acetyloxy-5',7,9,13-tetramethylspiro[5,16-dioxahexacyclo[10.9.0.02,9.04,8.013,19.015,17]henicosane-6,2'-oxane]-10-yl] acetate
  参考文献：
  名称：

  Synthesis and Biological Activity Of Unsymmetrical Bis-Steroidal Pyrazines Related to the Cytotoxic Marine Natural Product Cephalostatin 1

  摘要：

  A mild, high-yielding synthesis of symmetrical steroidal pyrazines was achieved from the dimerization of 2-amino-3-ketosteroids, which were produced in situ from the triphenylphosphine-water reduction of the corresponding alpha-azido ketone. 2-Azidocholestan-3-one gave the dimeric steroidal pyrazine very cleanly, and two known dimeric pyrazines based on androstanone were also made using this methodology. Both C-2-symmetric geometric isomers of the dimeric steroidal pyrazine derived from cholestane were prepared by reaction of 2,3-diaminocholestane with cholestane-2,3-dione. A route to unsymmetrical bis-steroidal pyrazines was based on the observation that alpha-acetoxy ketones react with alpha-amino oximes directly with no need for oxidation of intermediate dihydropyrazines. Heating either 2 beta,17 beta-dihydroxyandrostan-3-one diacetate or 2 beta,17 beta-dihydroxyhecogenin-3-one diacetate with 2-amino-3-methoxyiminocholestane in toluene at 145 degrees C gave the corresponding unsymmetrical pyrazine in moderate yield. Five of the steroidal pyrazines were evaluated in the National Cancer Institute's new in vitro, disease-oriented antitumor screen, but none showed sufficient activity to warrant in vivo investigation.

  DOI：

  10.1021/jo00101a052
• 作为产物：
  描述：

  龙舌兰皂苷乙酯 在 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 生成 3β-acetoxy-12β-hydroxy-5α,25R-spirostan
  参考文献：
  名称：

  使用三氟乙酰基三氟甲磺酸盐（TFAT）进行螺环酮开环的有效方案。

  摘要：

  [反应：见正文]通过与三氟乙酰基三氟甲磺酸盐（TFAT）反应，可以在非常温和的条件下平稳地实现甾体螺酮的开环。新的螺环酮开环方案可提供高收率的ω-三氟乙酰基乙烯基醚，避免了以前采用的剧烈反应条件带来的困难。

  DOI：

  10.1021/ol035284h

文献信息

• Reduction of steroidal ketones with amine—boranes
  作者：A. E. Leontjev、L. L. Vasiljeva、K. K. Pivnitsky

  DOI：10.1023/b:rucb.0000035660.32775.ab

  日期：2004.3

  Complexes of secondary amines with borane, R2NH·BH3, surpass sodium borohydride as reducing agents for saturated and unsaturated steroidal 3-, 12-, 17-, and 20-ketones as regards chemo- and regioselectivity and mildness of the reaction conditions. In the case of 12-ketones, stereoselectivity is also improved.

  就化学和区域选择性以及反应条件的温和性而言，仲胺与硼烷的配合物 R2NH·BH3 作为饱和和不饱和甾体 3-、12-、17- 和 20-酮的还原剂优于硼氢化钠。在 12-酮的情况下，立体选择性也得到改善。
• Microwave-Promoted Rearrangement of Hecogenin Derivatives into Cnor- D-homo Steroids
  作者：Zhou Huan、Yue Pei、Ruan Hanli、Zhang Yonghui、Pi Huifang、Zhang Peng、Wu Jizhou

  DOI：10.2174/157017809787582799

  日期：2009.3.1

  By means of microwave irradiation, the rearrangement from 12β-tosylate and 12β-alcohol of hecogenin derivatives into C-nor-D-homo-Δ17a(18)-olefin (2) and the Δ13(17a)-isomer (3) was achieved. With this method, the controlled solvolysis in anhydrous pyridine gave total conversion to desired exocyclic-olefin which is expected to be a building block of isosteroidal alkaloids.

  通过微波辐射，实现了血红素衍生物的12β-甲苯磺酸酯和12β-醇重排为C-nor-D-homo-Δ17a（18）-烯烃（2）和Δ13（17a）-异构体（3） 。用这种方法，在无水吡啶中的受控溶剂分解使全部转化为所需的环外烯烃，预期该环外烯烃是异甾体生物碱的组成部分。
• A Simple Four‐Step Synthesis of the Potato Alkaloid Demissidine from the Common Sapogenin Tigogenin
  作者：Aneta Baj、Nirawit Kaewnok、Juan A. Rivas‐Loaiza、Magdalena Szymańska、Stanisław Witkowski、Agnieszka Wojtkielewicz、Jacek W. Morzycki

  DOI：10.1002/chem.202203314

  日期：——

  A four-step synthesis of demissidine from tigogenin acetate was developed. The key-step of the synthesis was the epimerization at C25 of the lactam intermediate.

  开发了从醋酸替高皂甙四步合成去米西丁的方法。合成的关键步骤是内酰胺中间体在C25位的差向异构化。
• Steroidal Sapogenins^1a
  作者：Russell E. Marker、R. B. Wagner、Paul R. Ulshafer、Emerson L. Wittbecker、Dale P. J. Goldsmith、Clarence H. Ruof

  DOI：10.1021/ja01201a032

  日期：1947.9
• Steroidal Sapogenins. XXXV. Gentrogenin (Botogenin) and Correllogenin, New Sapogenins from Dioscorea spiculiflora^2,3,4
  作者：HENRY A. WALENS、SAMUEL SEROTA、MONROE E. WALL

  DOI：10.1021/jo01353a024

  日期：1957.2