5,6-epoxystigmast-22-en-3β-yl acetate | 107380-01-8

• 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: 5,6-epoxystigmast-22-en-3β-yl acetate
• 英文别名: 3-O-acetyl-5,6-epoxystigmast-22-en-3-ol；[(1S,2R,5S,11S,12S,15R,16R)-15-[(E,2R,5S)-5-ethyl-6-methylhept-3-en-2-yl]-2,16-dimethyl-8-oxapentacyclo[9.7.0.02,7.07,9.012,16]octadecan-5-yl] acetate
• CAS: 107380-01-8
• 化学式: C₃₁H₅₀O₃
• 分子量: 470.736
• InChiKey: JXMOTLXADPUXHB-XPMFSBJRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.58
• 重原子数：
  34.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  38.83
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  5,6-epoxystigmast-22-en-3β-yl acetate 在 高氯酸 、 pyridinium chlorochromate 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 (22E)-3β-acetoxy-5α-hydroxystigmast-22-en-6-one
  参考文献：
  名称：

  Synthesis and bioactivity evaluation of brassinosteroid analogs

  摘要：

  Four new analogs of 28-homocastasterone have been synthesized and completely characterized for the first time from stigmasterol. (22R,23R,24S)-3 beta-acetoxy-22,23-dihydroxy-5 alpha-stigmastan-6-one (17), (22R,23R,24S)-3 beta-bromo-22,23-dihydroxy-5 alpha-stigmastan-6-one (18), (22R,23R,24S)-3 beta-acetoxy-5,22,23-trihydroxy-5 alpha-stigmastan-6-one (20), and (22R,23R,24S)-3 beta-bromo-5,22,23-trihydroxy-5 alpha-stigmastan-6-one (21), were obtained through a synthetic route based on regioselective Delta(5) epoxidation. Compounds 17 and 18, bearing a 5 alpha H moiety, were prepared through a reductive opening of the 5 beta,6 beta epoxy precursor, and compounds 20 and 21, analogs with a 5 alpha OH moiety were obtained by hydrolytic opening of a mixture of 5 alpha,6 alpha and 5 beta,6 beta epoxy precursors. Known compounds 19 and 22 were also obtained following the described synthetic routes, respectively. The new compounds were tested with the traditional auxin-like bioassay for brassinosteroids with 19 and 22 as standards. All compounds were comparatively evaluated for their inhibitory effect on the replication of DNA (HSV-1) virus. (C) 2000 Elsevier Science Inc. All rights reserved.

  DOI：

  10.1016/s0039-128x(00)00093-3
• 作为产物：
  描述：

  24-ethyl-22-dehydrocholesterol acetate 以93%的产率得到
  参考文献：
  名称：

  KOVGANKO, N. V.;ANANICH, S. K., XIMIYA PRIROD. SOED.,(1989) N, S. 664-669

  摘要：

  DOI：

文献信息

• Quantitative Structure Inter-Activity Relationship (QSInAR). Cytotoxicity Study of Some Hemisynthetic and Isolated Natural Steroids and Precursors on Human Fibrosarcoma Cells HT1080
  作者：Mihai V. Putz、Marius Lazea、Louis P. Sandjo

  DOI：10.3390/molecules16086603

  日期：——

  Combined experimental and quantitative structure inter-activity relationship (QSIAR) computation methods were advanced in order to establish the structural and mechanistic influences that steroids and triterpenes, either as newly synthesized or naturally isolated products, have on human HT1080 mammalian cancer cells. The main Hansch structural indicators such as hydrophobicity (LogP), polarizability (POL) and total energy (Etot) were considered and both the structure-projected as well as globally computed correlations were reported; while the inter-activity correlation of the global activity with those projected on structural information was revealed as equal to the direct structural-activity one for the trial sets of compounds, the prediction for the testing set of molecules reported even superior performances respecting those characteristic for the calibration set, validating therefore the present QSInAR models; accordingly, it follows that the LogP carries the most part of the cytotoxic signal, while POL has little influence on inhibiting tumor growth—A complementary behavior with their earlier known influence on genotoxic carcinogenesis. Regarding the newly hemisynthetic compounds it was found that stigmasta-4,22-dien-3-one is not adapted for cell membrane diffusion; it is recommended that aminocinnamyl chlorohydrate be further modified in order to acquire better steric influence, while aminocinnamyl-2,3,4,6-O-tétraacétyl-α-D-glucopyranoside was identified as being inhibited in the tumor cell by other molecular mechanisms–here not revealed–although it has a moderate-high anti-cancer structurally predicted activity.

  为了确定类固醇和三萜类化合物（无论是新合成的还是天然分离的产品）对人类 HT1080 哺乳动物癌细胞的结构和机理影响，我们采用了实验和定量结构间活性关系（QSIAR）计算相结合的方法。我们考虑了主要的 Hansch 结构指标，如疏水度 (LogP)、极化性 (POL) 和总能 (Etot)，并报告了结构预测和全局计算的相关性；全局活性与根据结构信息预测的活性之间的相关性与试验组化合物的直接结构-活性之间的相关性相同，而对测试组分子的预测报告甚至优于校准组的预测报告，从而验证了目前的 QSInAR 模型；因此，LogP 带有大部分细胞毒性信号，而 POL 对抑制肿瘤生长的影响很小--这与早先已知的 POL 对基因毒性致癌的影响是互补的。关于新的半合成化合物，发现石杉碱甲-4,22-二烯-3-酮不适合细胞膜扩散；此外，还发现氨肉桂基-2,3,4,6-O-tétraacétyl-α-D-吡喃葡萄糖苷可通过其他分子机制抑制肿瘤细胞--在此尚未揭示--尽管从结构上预测其具有中等偏上的抗癌活性。
• Synthesis and Characterization of Stigmasterol Oxidation Products
  作者：David A. Foley、Yvonne O’Callaghan、Nora M. O’Brien、Florence O. McCarthy、Anita R. Maguire

  DOI：10.1021/jf9024745

  日期：2010.1.27

  The synthesis and structural characterization of a series of oxides of stigmasterol is described providing a valuable series of reference standards for these oxides, analogous to the cholesterol oxidation products (COPs) which have been shown to have detrimental biological effects. Biological evaluation of the oxides of phytosterols is significant in the context of increased dietary use of phytosterols

  描述了一系列豆甾醇的氧化物的合成和结构表征，为这些氧化物提供了一系列有价值的参考标准，类似于已证明具有有害生物作用的胆固醇氧化产物（COP）。在饮食中增加植物甾醇的使用以降低胆固醇吸收的情况下，对植物甾醇的氧化物的生物学评估是重要的。
• A concise synthesis of β-sitosterol and other phytosterols
  作者：Jiliang Hang、Patrick Dussault

  DOI：10.1016/j.steroids.2010.05.016

  日期：2010.12

  A convenient synthesis of sidechain-modified phytosterols is achieved via a temporary masking of the stigmasterol 5,6-alkene as an epoxide. Following performance of the desired modification, the alkene is regenerated through a mild deoxygenation. The approach is applied to the syntheses of beta-sitosterol and campesterol acetate, and suggests a facile route to the (Z)-isomers of Delta(22-23) phytosterols. (C) 2010 Elsevier Inc. All rights reserved.