23-oxo-hecogenin acetate | 366018-06-6

• 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: 23-oxo-hecogenin acetate
• 英文别名: 23-oxohecogenin acetate；[(1R,2S,4S,5'R,6S,7S,8R,9S,12S,13S,16S,18S)-5',7,9,13-tetramethyl-3',10-dioxospiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icosane-6,2'-oxane]-16-yl] acetate
• CAS: 366018-06-6
• 化学式: C₂₉H₄₂O₆
• 分子量: 486.649
• InChiKey: CQWFGOOIRQCLCK-LGWAINHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  35
• 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：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  23-oxo-hecogenin acetate 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (23Z,25R)-3β,26-diacetoxy-16β,23-epoxy-5α-cholest-23-ene-12,22-dione
  参考文献：
  名称：

  Regioselective cleavage of 22-oxo-23-spiroketals. Novel cholestanic frameworks with pyranone and cyclopentenone E rings on the side chain

  摘要：

  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.

  DOI：

  10.1016/j.steroids.2012.01.018
• 作为产物：
  描述：

  龙舌兰皂苷乙酯 在 silver tetrafluoroborate 、 溴 、 溶剂黄146 作用下， 以 乙二醇二甲醚 、 水 为溶剂， 反应 96.0h， 生成 23-oxo-hecogenin acetate
  参考文献：
  名称：

  辅助溶剂分解23-螺乙炔基溴化物和甲苯磺酸酯。螺旋烷的新重排至双呋喃系统。

  摘要：

  在多种条件下，通过涉及缩醛氧原子与邻位基团参与的核糖核酸离开C23的机制，在C23处带有良好离去基团的甾体类皂甙元经历了完全立体定向的重排。赤道的（23S）-23-溴-或（23S）-23-甲苯磺酰螺甾烷与α（25R）或β（25S）定向的25-甲基的反应导致双呋喃产物的C23构型反转。起始化合物与C23处的轴向取代基（23R）的反应需要严格的条件，并导致形成伴随重排产物的相应烯烃（仅在25S异构体的情况下）。

  DOI：

  10.1021/jo020231j

文献信息

• Novel transformation of 23-bromosapogenins. Synthesis of (22S,23R)-22-hydroxy-23,26-epoxyfurostanes
  作者：Jacek W Morzycki、Izabella Jastrzębska

  DOI：10.1016/s0040-4039(01)01165-0

  日期：2001.8

  (22S,23S)-23-Bromosapogenins undergo rearrangement to the (22S,23R)-22-hydroxy-23,26-epoxyfurostanes during alkaline hydrolysis. An efficient degradation procedure of sarsapogenin via the corresponding bisfuran to the C(22) lactone is described. (C) 2001 Elsevier Science Ltd. All rights reserved.

  （22S,23S）-23-溴野马沸苷在碱性水解过程中发生重排，生成（22S,23R）-22-羟基-23,26-环氧化呋甾烷。文中描述了一种通过相应双呋喃将萨斯波苷素高效降解为C（22）内酯的程序。（C）2001 Elsevier Science Ltd. 保留所有权利。
• 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.
• An Assisted Solvolysis of 23-Spirostanyl Bromides and Tosylates. A New Rearrangement of Spirostanes to the Bisfuran Systems
  作者：Romana Anulewicz-Ostrowska、Izabella Jastrzȩbska、Jacek W. Morzycki、Jacek Wójcik

  DOI：10.1021/jo020231j

  日期：2002.10.1

  Steroidal sapogenins bearing a good leaving group at C23 undergo a completely stereospecific rearrangement under a variety of conditions via a mechanism involving neighboring-group participation by the acetal oxygen atom in the departure of the nucleofuge from C23. The reactions of equatorial (23S)-23-bromo- or (23S)-23-tosyloxyspirostanes with either the alpha (25R) or beta (25S) oriented 25-methyl

  在多种条件下，通过涉及缩醛氧原子与邻位基团参与的核糖核酸离开C23的机制，在C23处带有良好离去基团的甾体类皂甙元经历了完全立体定向的重排。赤道的（23S）-23-溴-或（23S）-23-甲苯磺酰螺甾烷与α（25R）或β（25S）定向的25-甲基的反应导致双呋喃产物的C23构型反转。起始化合物与C23处的轴向取代基（23R）的反应需要严格的条件，并导致形成伴随重排产物的相应烯烃（仅在25S异构体的情况下）。
• 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.