(1S,10R)-3β-acetoxy-1,10-epoxy-5,10-secocholestane-5,6-lactone | 1393735-17-5

• 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: (1S,10R)-3β-acetoxy-1,10-epoxy-5,10-secocholestane-5,6-lactone
• 英文别名: [(1S,2R,4S,6S,12S,13S,16R,17R)-2,17-dimethyl-16-[(2R)-6-methylheptan-2-yl]-8-oxo-3,9-dioxatetracyclo[10.7.0.02,4.013,17]nonadecan-6-yl] acetate
• CAS: 1393735-17-5
• 化学式: C₂₉H₄₈O₅
• 分子量: 476.697
• InChiKey: LBBKESRXADEYBM-RFCYWISBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (1S,10R)-1,10-Epoxy-5-oxo-5,10-secocholestan-3β-yl acetate 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 192.0h， 以6%的产率得到[(1S,4S,5S,8R,9R,12S,13S,14S,16S)-9,13-dimethyl-8-[(2R)-6-methylheptan-2-yl]-18,19-dioxapentacyclo[11.4.1.11,14.04,12.05,9]nonadecan-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