(10S)-10-hydroperoxy-A-nor-5,10-secocholestan-2β-yl acetate | 1393735-20-0

• 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: (10S)-10-hydroperoxy-A-nor-5,10-secocholestan-2β-yl acetate
• 英文别名: [(1S,2S,5R,6R,9S,10S,12S)-10-hydroperoxy-6,10-dimethyl-5-[(2R)-6-methylheptan-2-yl]-14-oxo-12-tricyclo[7.7.0.02,6]hexadecanyl] acetate
• CAS: 1393735-20-0
• 化学式: C₂₈H₄₈O₅
• 分子量: 464.686
• InChiKey: XLKUBXZQJHUKIB-SDTSZYPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (E)-3β-acetoxy-5,10-seco-cholest-1(10)-en-5-one 在 disodium hydrogenphosphate 、 过氧化脲素 、 碳酸氢钠 、 间氯过氧苯甲酸 、 三氟乙酸酐 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 48.0h， 生成 (10S)-10-formyl-A-nor-5,10-secocholestan-2β-yl acetate 、 (1S,10R)-1,10-epoxy-A-nor-5,10-secocholestan-2β-yl acetate 、 (10S)-10-hydroperoxy-A-nor-5,10-secocholestan-2β-yl acetate 、 [(1R,2R,3S,6R,7R,10S,11S,13S,14S,16S)-14-hydroxy-2,6-dimethyl-7-[(2R)-6-methylheptan-2-yl]-18-oxapentacyclo[12.3.1.02,13.03,11.06,10]octadecan-16-yl] acetate
  参考文献：
  名称：

  Oxidative 10-membered ring expansion and contraction of stereoisomeric 1(10)-unsaturated and 1,10-epoxy-5-oxo-5,10-secosteroids induced by peracids

  摘要：

  The present study is concerned with the oxidative behaviour of unsaturated and epoxy 5-oxo-5,10-secosteroids in the presence of m-CPBA or TFAA-UHP as oxidants in order to investigate potential parameters controlling the chemoselectivity and regioselectivity. In the study we discovered a striking difference in the chemical behaviour of stereoisomeric compounds, (Z)- and (E)-3 beta-acetoxy-5,10-secocholest-1(10)-en-5-ones, as well as 1S,10R- and 1R,10R-epoxides. The secoketones were oxidized with exclusively C-6 migration and Baeyer-Villiger rearrangement product formation, whereas their stereoisomers provided the ring-contracted products, without lactone formation. The preferred conformation of expanded and contracted rings was established by NOESY correlations. The structures of two obtained lactones were also confirmed by X-ray analysis. The mechanistic and stereochemical aspects of these transformations are discussed. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.06.024