(23R,25R)-3β-acetoxy-16β,23:23,26-diepoxycholest-5-en-22-one | 213528-60-0

• 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-16β,23:23,26-diepoxycholest-5-en-22-one
• 英文别名: [(1S,2S,4S,4'R,6R,8S,9R,10S,13S,14R,17S)-4',8,10,14-tetramethyl-7-oxospiro[5-oxapentacyclo[11.8.0.02,10.04,9.014,19]henicos-19-ene-6,2'-oxolane]-17-yl] acetate
• CAS: 213528-60-0
• 化学式: C₂₉H₄₂O₅
• 分子量: 470.649
• InChiKey: WNOCKSVUHIBSQR-KHMABQDISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.86
• 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,25R)-3β-acetoxy-16β,23:23,26-diepoxycholest-5-en-22-one 在 sodium tetrahydroborate 、 二异丁基氢化铝 作用下， 以 吡啶 、 乙醇 为溶剂， 反应 25.17h， 生成 (22R,23R,25R)-3β-acetoxy-23,26-epoxyfurost-5-ene
  参考文献：
  名称：

  通过甾体螺缩醛的重排，立体定向合成1,6-二氧杂cal呤和2,2'-连接的四氢呋喃。

  摘要：

  用DIBALH还原包含1,6-dioxaspiro [4.5] decan-10-yl环系统的甾体螺缩醛甲磺酸衍生物，可促进新的重排，从而得到甾体1,6-二氧杂ade环素（八氢吡喃并[3,2-b]吡喃）或2,2'-连接的二四氢呋喃（八氢[2,2']双呋喃基）衍生物。为了研究反应的范围和选择性，使用了几种甾体螺缩醛，例如（23R，25R）-3beta-甲氧基-5alpha-spirostan-23-甲磺酸盐（2）及其23S-异构体（5）和（22R，23R，已经合成了甲磺酸25R）-3β-乙酰氧基-16β，23：23,26-二乙氧基胆甾-5-en-22-基（15）及其22S-异构体（19）。以绝对的区域和立体选择性重排化合物2，得到（22S，23S，25R）-3β-甲氧基-16β，23：22,26-二环氧-5α-胆甾烷（3），其具有顺式稠合的1,6- dioxadecalin环系统。化合物5的

  DOI：

  10.1021/jo980834o
• 作为产物：
  描述：

  (25R)-3β-acetoxyspirost-5-en-23-one 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 生成 (23R,25R)-3β-acetoxy-16β,23:23,26-diepoxycholest-5-en-22-one
  参考文献：
  名称：

  通过甾族螺缩醛的重排，顺式和反式融合的Di-tetrahydropyrans

  摘要：

  描述了一种新的合成甾体顺式和反式融合的二-四氢吡喃（1,6-二氧杂萘烷）的新方法，该方法通过DIBAH还原1,6-二氧杂螺并[4,5]癸十烷基甲磺酸酯的衍生物而得到。

  DOI：

  10.1016/0040-4039(95)01472-t

文献信息

• 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。
• 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.
• 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.
• Rearrangement of 23-oxospirostanes to the 22-oxo-23-spiroketal isomers promoted by Lewis acids—X-ray crystal structure of (23R,25S)-3β-acetoxy-16β,23:23,26-diepoxy-5β-cholestan-22-one
  作者：Michał K. Cyrański、Jadwiga Frelek、Izabella Jastrzębska、Jacek W. Morzycki

  DOI：10.1016/j.steroids.2004.03.010

  日期：2004.6

  Both 25R and 25S 23-oxospirostanes undergo rearrangement to the 22-oxo-23-spiroketal isomers promoted by Lewis acids. An X-ray crystal structure analysis of the rearranged product of 23-oxosarsasapogenin acetate confirmed the R configuration at the new spiro carbon atom. (C) 2004 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.