(23R,25S)-3β-acetoxy-16β,23:23,26-diepoxy-5β-cholestan-22-one | 914477-77-3

• 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,25S)-3β-acetoxy-16β,23:23,26-diepoxy-5β-cholestan-22-one
• 英文别名: [(1R,2S,4S,4'S,6R,8S,9R,10S,13S,14S,17S,19R)-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: 914477-77-3
• 化学式: C₂₉H₄₄O₅
• 分子量: 472.665
• InChiKey: YCSUZCGVZXOVDX-GAFCPQCYSA-N

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：

  (23R,25S)-3β-acetoxy-16β,23:23,26-diepoxy-5β-cholestan-22-one 在 三氟化硼乙醚 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以63.6%的产率得到3β-acetoxy-16β-hydroxy-5β-bisnorcholanoic acid 22->16 lactone
  参考文献：
  名称：

  Studies on the BF3·Et2O catalyzed Baeyer–Villiger reaction of spiroketalic steroidal ketones

  摘要：

  During reactions of 23-oxosapogenins and the corresponding isomeric 22-oxo-23-spiroketals with MCPBA in the presence of BF3 center dot Et2O, equilibration occurs between the ketones. The Baeyer-Villiger type oxidation is followed by fragmentation to the dinorcholanic lactones and 3-methylbutyrolactone. The mechanistic aspects of these reactions in the 25R and 25S series are discussed. (C) 2010 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2010.12.004
• 作为产物：
  描述：

  sarsasapogenin acetate 在 三氟化硼乙醚 、 四氯化钛 、 sodium nitrite 作用下， 以 二氯甲烷 、 水 、 溶剂黄146 为溶剂， 生成 (23R,25S)-3β-acetoxy-16β,23:23,26-diepoxy-5β-cholestan-22-one
  参考文献：
  名称：

  New bisfuran derivative from sarsasapogenin

  摘要：

  The new bisfuran derivative, (22S,23S)-22,23-dihydroxy-23,26-epoxyfurostane (5), was obtained from the known oxidation of sarsasapogenin acetate with NaNO2/BF3 in 5% aqueous acetic acid. The structure of 5 was established using one and two-dimensional H-1, C-13 experiments (DEPT, COSY, HETCOR and HMBC) and the configurations at the newly formed stereogenic centers were established as 22S,23S by an X-ray diffraction analysis. Addition of TiCl4 to bisfuran 5 confirmed that this compound is an intermediate in the rearrangement to 22-oxo-23-spiroketals since it was transformed quantitatively into the latter product. The 23-nitroimino intermediate 2 was isolated from the same reaction and its structure established also by an X-ray diffraction analysis; this compound was further transformed into the 23-nitramine 7 which could find application in functionalization of position 24. (c) 2005 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2005.07.009

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。
• 1H and 13C NMR characteristics of synthetic derivatives of steroid sapogenins
  作者：Ignacio Vázquez-Ramírez、Mariana Macías-Alonso、Rafael O. Arcos-Ramos、Karen M. Ruíz-Pérez、Diana O. Solano-Ramírez、Martín A. Iglesias Arteaga

  DOI：10.1016/j.steroids.2008.01.027

  日期：2008.7

  The full assignments of the (1)H and (13)C NMR signals of steroids bearing the 16beta,23:23,26-diepoxy side chain are provided. Differentiation of the diasterotopic H-26 pair was achieved with the aid of NOESY experiments. The main substituent and steric effects associated with this moiety and their influence on the chemical shifts of the neighboring atoms are discussed.

  提供了带有 16beta,23:23,26-diepoxy 侧链的类固醇的 (1) H 和 (13) C NMR 信号的完整分配。在 NOESY 实验的帮助下实现了非对映体 H-26 对的分化。讨论了与该部分相关的主要取代基和空间效应及其对相邻原子化学位移的影响。
• Regio- and stereoselective cleavage of steroidal 22-oxo-23-spiroketals catalyzed by BF3·Et2O
  作者：Alejandro Corona Díaz、J. Pablo García Merinos、Yliana López、J. Betzabe González Campos、Rosa E. del Río、Rosa Santillan、Norberto Farfán、Jacek W. Morzycki

  DOI：10.1016/j.steroids.2015.04.004

  日期：2015.8

  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.
• Regioselective cleavage of 22-oxo-23-spiroketals. Novel cholestanic frameworks with pyranone and cyclopentenone E rings on the side chain
  作者：Yliana López、León Rodríguez、Rosa E. del Río、Norberto Farfán、Jacek W. Morzycki、Rosa Santillan

  DOI：10.1016/j.steroids.2012.01.018

  日期：2012.4

  The regioselective opening of the F ring of 22-oxo-23-spiroketals using a saturated solution of HCl in acetic anhydride yielded novel cholestanic frameworks with pyranone or cyclopentenone E rings. The structures of the new derivatives of sarsasapogenin, diosgenin and hecogenin thus obtained were established using one and two dimensional H-1, C-13 experiments (DEPT, COSY, HETCOR, HMBC, ROESY, and NOESY). The X-ray analysis for compound lib confirmed the 23R configuration for the new stereogenic center. (C) 2012 Elsevier Inc. All rights reserved.