3β-acetoxy-12α-hydroxy-5α-spirostan-14-ene | 78179-60-9

• 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: 3β-acetoxy-12α-hydroxy-5α-spirostan-14-ene
• 英文别名: (25R)-3β-Acetoxy-5α-spirost-14-en-12α-ol；[(1R,4S,5'R,6R,7S,8R,9R,10S,12S,13S,16S,18S)-10-hydroxy-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icos-2-ene-6,2'-oxane]-16-yl] acetate
• CAS: 78179-60-9
• 化学式: C₂₉H₄₄O₅
• 分子量: 472.665
• InChiKey: BAVBQJHNDDYUAA-SYHJYGTOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3β-acetoxy-12α-hydroxy-5α-spirostan-14-ene 在 氢氧化钾 、 2,6-二叔丁基吡啶 、 dimethyl sulfide borane 、 苯基锂 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 环己烷 为溶剂， 反应 12.0h， 生成 (3β,5α,12β,25R)-3-methoxyspirost-14-ene-12-methanol
  参考文献：
  名称：

  Synthesis of Cytostatic Tetradecacyclic Pyrazines and a Novel Reduction-Oxidation Sequence for Spiroketal Opening in Sapogenins

  摘要：

  Aiming towards spiroketal-modified artificial cephalostatin molecules, two orthogonal approaches were investigated. First, the introduction of 17-O-functionality into hecogenin derivatives with a closed spiroketal moiety was accomplished by different remote-oxidation procedures. These allowed the synthesis of tetradecacyclic artificial cephalostatin molecules with improved tumor-inhibiting properties. Second, a novel reduction-oxidation pathway for spiroketal opening in sapogenins was discovered, which should provide the basis for a broad access towards spiroketal-modified building blocks for cephalostatins.

  DOI：

  10.1002/1522-2675(20000809)83:8<1854::aid-hlca1854>3.0.co;2-4
• 作为产物：
  描述：

  龙舌兰皂苷乙酯 在 三氟化硼乙醚 作用下， 以 1,4-二氧六环 、 甲苯 为溶剂， 反应 6.5h， 生成 3β-acetoxy-12α-hydroxy-5α-spirostan-14-ene
  参考文献：
  名称：

  Ritterazines B、F、G 和 H 的东半部分的合成，导致 Ritterazines B 和 F 的 5,5-Spiroketal 立体化学的重新分配

  摘要：

  利特嗪类天然产物包含 26 种化合物——所有这些化合物都是含有螺缩酮的甾体异二聚体——它们抑制培养的人类癌细胞系的增殖，IC50 值在低纳摩尔范围内。对它们的化学、细胞靶标或生长抑制机制知之甚少，主要是由于可从天然来源获得的材料量很少。在本文中，我们报告了利特拉嗪 B、F、G 和 H 的东半部的合成，并解决了每个 spiroketal 平衡的能量和机械方面。这些研究导致了利特嗪 B 和 F 的 5,5-螺酮立体化学的重新分配，并且它们使我们能够提出这些利特嗪化合物的自然分布的定量描述。

  DOI：

  10.1021/ja0705487

文献信息

• Redox Refunctionalization of Steroid Spiroketals. Structure Correction of Ritterazine M
  作者：Seongmin Lee、Thomas G. LaCour、Douglas Lantrip、Philip L. Fuchs

  DOI：10.1021/ol0165894

  日期：2002.2.1

  The structure of the North spiroketal moiety of ritterazine M has been corrected from 1a to 1b. This was accomplished by comparison of published spectra of the natural product with five synthetic spiroketal-alcohols. Synthesis of these models was efficiently accomplished by reductive cleavage of the spiroketal and Sharpless asymmetric dihydroxylation of an isopentyl, methyl 1,1-disubstituted olefin

  利他嗪M的北部螺环结构的结构已从1a修正为1b。这是通过比较已公开的天然产物光谱与五种合成螺酮醇来完成的。这些模型的合成是通过以下方法有效地完成的：首先对异戊基甲基1,1-二取代的烯烃进行螺环的还原裂解和Sharpless不对称二羟基化反应，然后对Suarez碘[III]进行单保护的1度，3度1,2二醇的氧化螺环化反应。
• Transetherification-mediated E-ring opening and stereoselective “Red-Ox” modification of furostan
  作者：Young Cheun、Myong Chul Koag、Yi Kou、Zachary Warnken、Seongmin Lee

  DOI：10.1016/j.steroids.2011.12.015

  日期：2012.2

  We have developed a novel E-ring opening method for furostan, and applied it to prepare D-ring modified steroids, which can be used to synthesize cephalostatin analogs. (C) 2011 Elsevier Inc. All rights reserved.
• Synthesis of 14′,15′-dehydro-ritterazine Y via reductive and oxidative functionalizations of hecogenin acetate
  作者：Yi Kou、Young Cheun、Myong Chul Koag、Seongmin Lee

  DOI：10.1016/j.steroids.2012.10.021

  日期：2013.2

  An analog of ritterazine Y was synthesized from hecogenin acetate in 23 steps via functional group manipulations of hecogenin acetate. Preparation of the north G and south Y units and the late stage Guo-Fuchs asymmetric coupling of the both units afforded the ritterazine Y analog. (C) 2012 Elsevier Inc. All rights reserved.
• Welzel, Peter; Janssen, Bernd; Duddeck, Helmut, Liebigs Annalen der Chemie, 1981, # 3, p. 546 - 564
  作者：Welzel, Peter、Janssen, Bernd、Duddeck, Helmut

  DOI：——

  日期：——
• Photochemistry of Hecogenine Acetate Revisited
  作者：R. Jautelat、E. Winterfeldt、A. M�ller-Fahrnow

  DOI：10.1002/prac.199633801137

  日期：——

  We were successful in optimizing the synthesis of the homoallylic alcohol 6 from hecogenine acetate 2 as an important precursor for our approach to cephalostatin analogues by doubling the yields. On this way we discovered that formation of homoallylic alcohol 6 proceeds via a diastereoselective intramolecular Lewis acid catalysed ene reaction directly from lumihecogenine acetate 3. Finally we were able to elucidate the structure of the already described but not clearly identified oxa-dimer 7.