pseudodiosgenin diacetate | 2309-38-8

• 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: pseudodiosgenin diacetate
• 英文别名: pseudodiosgenin 3β,26-diacetate；[(2R)-4-[(1S,2S,4S,8S,9S,12S,13R,16S)-16-acetyloxy-7,9,13-trimethyl-5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icosa-6,18-dien-6-yl]-2-methylbutyl] acetate
• CAS: 2309-38-8
• 化学式: C₃₁H₄₆O₅
• 分子量: 498.703
• InChiKey: SYAZYBRDBNTORM-RVGNKCLJSA-N

物化性质

• 熔点：
  97-101 °C
• 沸点：
  574.4±50.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.81
• 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：

  pseudodiosgenin diacetate 在 chromium(VI) oxide 、 盐酸 、 乙醇 、 sodium 、 溶剂黄146 作用下， 生成 20α,3β-Di-acetoxy-Δ⁵-pregnen
  参考文献：
  名称：

  Sterols. CXVII. Sapogenins. XLVI. The Structure of Pseudosapogenins

  摘要：

  DOI：

  10.1021/ja01848a039
• 作为产物：
  描述：

  (22R,25S)-22-hydroxyfurost-5-ene-3β,26-diyl diacetate 在 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以88%的产率得到pseudodiosgenin diacetate
  参考文献：
  名称：

  室温下spirostans快速转化为furostan骨架

  摘要：

  我们报告了一种简便的方案，可从 (25R)-和 (25S)-皂苷元中以高产率获得 22-取代呋喃丹和假皂苷元。该方法包括在室温下用乙酸-三氟乙酸混合酸酐和 BF(3)·OEt(2) 处理皂苷元，然后加入亲核试剂（H(2)O、MeOH 或 KSeCN）。在 22-羟基呋喃丹的情况下，它们可以通过用对甲苯磺酸处理转化为假皂苷元。

  DOI：

  10.1016/j.steroids.2011.10.004

文献信息

• 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。
• Synthesis of steroidal derivatives containing substituted, fused and spiro pyrazolines
  作者：Anabel Romero-López、Sara Montiel-Smith、Socorro Meza-Reyes、Penélope Merino-Montiel、José Luis Vega-Baez

  DOI：10.1016/j.steroids.2014.05.013

  日期：2014.9

  through a cycloaddition reaction of different α,β-unsaturated ketones with hydrazine acetate in acetic acid is reported. Depending on the starting material, the ring closure reaction provided a mixture of two steroidal pyrazoline epimers that were separated and studied by NMR techniques. In one case it was possible to isolate and characterize the hydrazone derivative as the reaction intermediate, which

  报道了通过不同 α,β-不饱和酮与乙酸肼在乙酸中的环加成反应，高效、简便地合成稠合、取代和螺吡唑啉类固醇衍生物。取决于起始材料，闭环反应提供了两种甾体吡唑啉差向异构体的混合物，通过 NMR 技术将其分离和研究。在一种情况下，可以将腙衍生物作为反应中间体进行分离和表征，这证实了文献 [11,25,26] 中提出的机制。
• Synthesis and Evaluation of Pyrimidine Steroids as Antiproliferative Agents
  作者：Alejandra Cortés-Percino、José Luis Vega-Báez、Anabel Romero-López、Adrián Puerta、Penélope Merino-Montiel、Socorro Meza-Reyes、José M. Padrón、Sara Montiel-Smith

  DOI：10.3390/molecules24203676

  日期：——

  A small and focused library of steroidal non-fused and fused pyrimidines was prepared from pregnenolone acetate and diosgenin, respectively. The key step was the cycloaddition reaction of nitrogen-containing 1,3-binucleophiles with the steroidal α,β-unsaturated ketone. Urea, thiourea and guanidine reacted in a similar manner and afforded the steroidal pyrimidines in good yields. The antiproliferative

  分别从醋酸孕烯醇酮和薯蓣皂苷元制备了一个小而集中的甾体非稠合嘧啶和稠合嘧啶文库。关键步骤是含氮 1,3-双亲核试剂与甾体 α,β-不饱和酮的环加成反应。尿素、硫脲和胍以类似的方式反应并以良好的产率提供甾体嘧啶。针对人类肿瘤细胞系的抗增殖试验给出了微摩尔范围内的 GI50 值，并且对健康的成纤维细胞没有影响。额外的实验表明，这些化合物不作为 P-糖蛋白底物，从而避免了耐药性的增加。由于其在低微摩尔范围内的强抗增殖活性，稠合甾体嘧啶硫酮被选为用于进一步测试的药物先导物。
• Continuous Flow Synthesis of 16-Dehydropregnenolone Acetate, a Key Synthon for Natural Steroids and Drugs
  作者：Valentina Mancino、Bruno Cerra、Alessandro Piccinno、Antimo Gioiello

  DOI：10.1021/acs.oprd.8b00038

  日期：2018.5.18

  multistep process to provide the continuous delivery of 16-dehydropregnenolone acetate (16-DPA) from diosgenin is described. The method was evaluated through batch screenings that helped to identify critical bottlenecks and flowability, and the best conditions were optimized in flow systems before the individual steps were telescoped together into a single integrated flow process. Further highlights of

  描述了一种伸缩的多步骤方法，用于从薯os皂苷元连续递送乙酸16-脱氢孕烯醇酮（16-DPA）。通过分批筛选评估了该方法，该筛选有助于确定关键瓶颈和流动性，并且在将各个步骤一起伸缩到单个集成流动过程之前，在流动系统中优化了最佳条件。我们方法的进一步亮点包括使用高效的在线萃取操作和反应监控，避免了步骤之间的耗时纯化以及提高效率和安全标准。
• Studies on the coloration mechanism of furostanol derivatives with Ehrlich reagent. I. On the reaction of 3,26-dimethoxy-furost-5,20-diene with Ehrlich reagent.
  作者：TENJI KONISHI、SHIU KIYOSAWA、JUNZO SHOJI

  DOI：10.1248/cpb.32.2111

  日期：——

  From the reddish reaction mixture of 3, 26-dimethoxy-furost-5, 20-diene (ψ-diosgenin dimethyl ether, 2) with Ehrlich reagent, a colorless condensation product was isolated and characterized as 3, 26-dimethoxy-23-(p-dimethylaminobenzylidenyl)-furost-5, 20-diene (3). However, a coexisting red product could not be isolated because of its instability. On treatment with dried hydrogen chloride or conc. hydrochloric acid, the colorless chloroform solution of 3 readily changed into a reddish solution, which was reversibly decolorized on addition of 3% ammonia-chloroform solution. Based on ultraviolet and carbon-13 nuclear magnetic resonance spectral analysis, the coloration mechanism of 2 with Ehrlich reagent has been inferred to be as follows. The reaction is initiated by condensation between p-dimethylaminobenzaldehyde and 2 to form 3, followed by protonation to form an iminium cation (3B) under acidic conditions.

  从3, 26-二甲氧基-呋喃酯-5, 20-二烯（ψ-地黄苷的二甲基醚，2）与厄尔利希试剂的红色反应混合物中，分离得到了无色的缩合产物，并将其表征为3, 26-二甲氧基-23-(对-二甲氨基苯亚基)-呋喃酯-5, 20-二烯（3）。然而，由于其不稳定性，无法分离出共存的红色产物。在与干燥的氯化氢或浓盐酸处理后，3的无色氯仿溶液迅速变为红色溶液，随后在加入3%的氨-氯仿溶液后可逆性去色。基于紫外光和碳-13核磁共振光谱分析，推测2与厄尔利希试剂的着色机制如下：反应由对-二甲氨基苯甲醛与2的缩合反应开始形成3，随后在酸性条件下发生质子化形成亚胺阳离子（3B）。