3β-acetoxy-12-keto-5α-spirostan-14-ene | 78179-61-0

• 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-12-keto-5α-spirostan-14-ene
• 英文别名: [(1R,4S,5'R,6R,7S,8R,9R,12S,13S,16S,18S)-5',7,9,13-tetramethyl-10-oxospiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icos-2-ene-6,2'-oxane]-16-yl] acetate
• CAS: 78179-61-0
• 化学式: C₂₉H₄₂O₅
• 分子量: 470.649
• InChiKey: VTFWGGXFLQHADH-DRRUTAESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  3β-acetoxy-12-keto-5α-spirostan-14-ene 在 氢氧化钾 、 2,6-二叔丁基吡啶 、 dimethyl sulfide borane 、 苯基锂 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：

  [(1R,2S,4S,5'R,6R,7S,8R,9S,12S,13S,16S,18S)-2,10-dihydroxy-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icosane-6,2'-oxane]-16-yl] acetate 在 吡啶 、 氯化亚砜 、 jones reagent 作用下， 生成 3β-acetoxy-12-keto-5α-spirostan-14-ene
  参考文献：
  名称：

  Interphylal Product Splicing:  The First Total Syntheses of Cephalostatin 1, the North Hemisphere of Ritterazine G, and the Highly Active Hybrid Analogue, Ritterostatin G_N1_N¹

  摘要：

  Convergent total syntheses of the extremely potent cell growth inhibitor cephalostatin 1 and two hybrid analogues, ritterostatins G(N)1(N) and G(N)1(S), have been achieved. Ritterostatin G(N)1(N) displays sub-nanomolar activity in the 60 cell line human tumor panel of the National Cancer Institute. The North hemisphere of ritterazine G was efficiently constructed from hecogenin acetate in 15% yield over 13 steps. Extension of a key photolysis/Prins sequence to intermediates 19 and 32 proceeded in excellent yield, leading to installation of the Delta(14) moiety in the-North G-and South I steroidal subunits. Application of a method for directed unsymmetrical coupling furnished the natural and analogue pyrazines in good yield from the cephalostatin and ritterazine components.

  DOI：

  10.1021/ja972160p

文献信息

• Syntheses of the Eastern Halves of Ritterazines B, F, G, and H, Leading to Reassignment of the 5,5-Spiroketal Stereochemistry of Ritterazines B and F
  作者：Scott T. Phillips、Matthew D. Shair

  DOI：10.1021/ja0705487

  日期：2007.5.1

  The ritterazine class of natural products comprises 26 compounds-all of which are spiroketal-containing steroidal heterodimers-that inhibit the proliferation of cultured human cancer cell lines with IC50 values in the low nanomolar range. Little is known about their chemistry, cellular target(s), or mechanism(s) of growth inhibition, due primarily to the small amount of material available from natural

  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。
• 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：——