22-epi-diosgenin acetate

• 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: 22-epi-diosgenin acetate
• 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'-oxane]-16-yl] acetate
• 化学式: C₂₉H₄₄O₄
• 分子量: 456.666
• InChiKey: CZCROZIJKBXZDP-RJDNYFEXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  33
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  22-epi-diosgenin acetate 在 三氟化硼乙醚 作用下， 以 氯仿 为溶剂， 反应 0.5h， 生成 薯蓣皂素乙酸盐
  参考文献：
  名称：

  （25R）-和（25S）-皂苷元中C-22的差向异构化。

  摘要：

  大多数天然存在的甾体皂苷元（C-23未取代的骨架）在螺C-22中心具有R构型。他们的C-22差向异构体已成为生物学研究的重要目标。本文介绍了一种在不影响C-25或C-20的手性的情况下，从22R-sapogenins和拟sapogenin骨架获得22S-spirostans的方法。还报道了合成23-乙酰二黄精苷的一对C-22立体异构体的最佳方法。后者是从22,26-环氧胆甾烷或23-乙酰基呋喃丁烯化合物获得的。

  DOI：

  10.1016/j.steroids.2014.10.004
• 作为产物：
  描述：

  [(1S,2S,4S,5'R,6R,7S,8R,9S,12S,13R,16S)-3'-hydroxy-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icos-18-ene-6,2'-oxane]-16-yl] acetate 在 咪唑 、 三正丁基氢锡 、 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 3.83h， 生成 22-epi-diosgenin acetate
  参考文献：
  名称：

  Photoinduced Isomerization of 23-Oxosapogenins: Conformational Analysis and Spectroscopic Characterization of 22-Isosapogenins

  摘要：

  The first synthesis of 22-isospirostane derivatives is described. They were obtained by photochemical isomerization of 23-oxosapogenins. The structure of 23-oxo-22-isotigogenin acetate (12) was proved by a single crystal X-ray diffraction, while structures of 23-oxo-22-isodiosgenin acetate (13) and 23-oxo-22-isosarsasapogenin acetate (14) were elucidated by spectroscopic methods. 22-Isodiosgenin acetate (17) was obtained by NaBH4 reduction of the 23-oxo derivative 13 followed by the two-step Barton-McCombie deoxygenation procedure. Conformational analysis of 22-iso compounds was carried out with CD and NMR, as well as DFT calculations.

  DOI：

  10.1021/jo3022549

文献信息

• Copper-catalysed allylic oxidation of Δ5-steroids by t-butyl hydroperoxide
  作者：J.A.R. Salvador、M.L. Sáe Melo、A.S. Campos Neves

  DOI：10.1016/s0040-4039(96)02231-9

  日期：1997.1

  Δ5-7-Oxosteroids are efficiently prepared from Δ5-steroids with t-BuOOH and a copper catalyst, either Cu(II) and Cu (I) salts or Cu metal; selectivity in the presence of a secondary alcohol is observed.

  Δ 5 -7- Oxosteroids有效地从制备Δ 5个-steroids与吨-BuOOH和铜催化剂，无论是铜（II）和Cu（I）盐或铜金属; 在仲醇存在下观察到选择性。
• Design and synthesis of diosgenin derivatives as apoptosis inducers through mitochondria-related pathways
  作者：Liwei Ma、Jinling Zhang、Xuemei Wang、Jifang Yang、Lina Guo、Xiaoli Wang、Bo Song、Wei Dong、Wenbao Wang

  DOI：10.1016/j.ejmech.2021.113361

  日期：2021.5
• MCGARTHY, PETER A., J. LABELL. COMPOUNDS AND RADIOPHARM., 28,(1990) N0, C. 1149-1159
  作者：MCGARTHY, PETER A.

  DOI：——

  日期：——
• Epimerization of C-22 in (25R)- and (25S)-sapogenins
  作者：Omar Viñas-Bravo、Penélope Merino-Montiel、Anabel Romero-López、Sara Montiel-Smith、Socorro Meza-Reyes、Francisco J. Meléndez、Jesús Sandoval-Ramírez

  DOI：10.1016/j.steroids.2014.10.004

  日期：2015.1

  Most of the naturally occurring steroidal sapogenins (C-23 non-substituted frameworks), possess an R configuration at the spiro C-22 center. Their C-22 epimers have become important targets in biological research. This paper describes a procedure to obtain 22S-spirostans from 22R-sapogenins and pseudosapogenin skeletons, without affecting the chirality at either C-25 or C-20. An optimal way to synthesize

  大多数天然存在的甾体皂苷元（C-23未取代的骨架）在螺C-22中心具有R构型。他们的C-22差向异构体已成为生物学研究的重要目标。本文介绍了一种在不影响C-25或C-20的手性的情况下，从22R-sapogenins和拟sapogenin骨架获得22S-spirostans的方法。还报道了合成23-乙酰二黄精苷的一对C-22立体异构体的最佳方法。后者是从22,26-环氧胆甾烷或23-乙酰基呋喃丁烯化合物获得的。
• Photoinduced Isomerization of 23-Oxosapogenins: Conformational Analysis and Spectroscopic Characterization of 22-Isosapogenins
  作者：Izabella Jastrzębska、Marcin Górecki、Jadwiga Frelek、Rosa Santillan、Leszek Siergiejczyk、Jacek W. Morzycki

  DOI：10.1021/jo3022549

  日期：2012.12.21

  The first synthesis of 22-isospirostane derivatives is described. They were obtained by photochemical isomerization of 23-oxosapogenins. The structure of 23-oxo-22-isotigogenin acetate (12) was proved by a single crystal X-ray diffraction, while structures of 23-oxo-22-isodiosgenin acetate (13) and 23-oxo-22-isosarsasapogenin acetate (14) were elucidated by spectroscopic methods. 22-Isodiosgenin acetate (17) was obtained by NaBH4 reduction of the 23-oxo derivative 13 followed by the two-step Barton-McCombie deoxygenation procedure. Conformational analysis of 22-iso compounds was carried out with CD and NMR, as well as DFT calculations.