(25R)-3β-Acetoxy-14-hydroxy-5α,14β-spirostan-12-on | 78216-38-3

• 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: (25R)-3β-Acetoxy-14-hydroxy-5α,14β-spirostan-12-on
• 英文别名: [(1R,2S,4S,5'R,6R,7S,8R,9R,12S,13S,16S,18S)-2-hydroxy-5',7,9,13-tetramethyl-10-oxospiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icosane-6,2'-oxane]-16-yl] acetate
• CAS: 78216-38-3
• 化学式: C₂₉H₄₄O₆
• 分子量: 488.665
• InChiKey: GZPLCVOMYLYDKX-SPNCQTHHSA-N

物化性质

• 沸点：
  589.5±50.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  35
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  82.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (25R)-3β-Acetoxy-14-hydroxy-5α,14β-spirostan-12-on 在 4-二甲氨基吡啶 、 氢氧化钾 、 氯化亚砜 、 三氟化硼 、 一水合肼 、 间氯过氧苯甲酸 作用下， 以 吡啶 、 乙醚 、 苯 为溶剂， 反应 93.08h， 生成 (25R)-3β-Acetoxy-14-fluor-5α-spirostan-15β-ol
  参考文献：
  名称：

  Welzel, Peter; Janssen, Bernd; Duddeck, Helmut, Liebigs Annalen der Chemie, 1981, # 3, p. 546 - 564

  摘要：

  DOI：
• 作为产物：
  描述：

  龙舌兰皂苷乙酯 在 jones reagent 、 溶剂黄146 作用下， 反应 24.0h， 生成 (25R)-3β-Acetoxy-14-hydroxy-5α,14β-spirostan-12-on
  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

• Ruthenium-Catalyzed Mild C−H Oxyfunctionalization of Cyclic Steroidal Ethers¹
  作者：Jong Seok Lee、Hui Cao、Philip L. Fuchs

  DOI：10.1021/jo070382s

  日期：2007.7.1

  Ruthenium-catalyzed site-specific C−H oxyfunctionalization of steroidal ethers with periodate or bromate as terminal oxidants in phosphate buffer provided the acid-sensitive C-16 hydroxy compounds in high yields. Phosphate buffer (pH 7.5) significantly inhibits formation of unwanted side products generated under more acidic reaction conditions. A key example is demonstrated at the 100 g scale.

  钌在磷酸盐缓冲液中以高碘酸盐或溴酸盐为末端氧化剂对甾族醚的钌催化位点特异性C-H羟基官能化提供了高收率的酸敏感性C-16羟基化合物。磷酸盐缓冲液（pH 7.5）可以显着抑制在更酸性的反应条件下生成的有害副产物的形成。以100克规模展示了一个关键的例子。
• New Oxidative Tools for the Functionalization of the Cephalostatin North 1 Hemisphere
  作者：Jong Seok Lee、Philip L. Fuchs

  DOI：10.1021/ol034551g

  日期：2003.6.1

  Dimethyldioxirane (DMDO) C-H oxidation of ketone 17 to hemiketal 18 (82%), bis-dehydration to vinyl ether 21 (77%), and DMDO again provides C-23 axial alcohol 23 (99%). Routine processing, Including a double-stereoselective Sharpless AD reaction (de >98%), gives alcohols 7 and 32. C-23 deoxy substrate 7 undergoes Suarez hypoiodite oxidative cyclization to (natural) beta spiroketal 34, but compound 32, bearing a C-23 silyl ether, generates unnatural spiroketal 33.
• An Efficient C−H Oxidation Protocol for α-Hydroxylation of Cyclic Steroidal Ethers
  作者：Seongmin Lee、Philip L. Fuchs

  DOI：10.1021/ol049712a

  日期：2004.4.1

  Various C-16 hydroxy steroids have been prepared with the aid of CrO3/Bu4NIO4. Out of the two possible reaction courses, transition state B is favored because of less steric interference between substrate and CrO4. Thus, C-H bonds at C-16 are oxidized selectively.