4-phenyl-1,1-bis[(triethylsilyl)dioxy]cyclohexane | 960121-27-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-phenyl-1,1-bis[(triethylsilyl)dioxy]cyclohexane
• 英文别名: Triethyl-(4-phenyl-1-triethylsilylperoxycyclohexyl)peroxysilane
• CAS: 960121-27-1
• 化学式: C₂₄H₄₄O₄Si₂
• 分子量: 452.782
• InChiKey: PGTPLOWLVKKZAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.95
• 重原子数：
  30
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-phenyl-1,1-bis[(triethylsilyl)dioxy]cyclohexane 、 亚甲基环己烷 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 以88%的产率得到11-Phenyl-14,15-dioxadispiro[5.1.58.26]pentadecane
  参考文献：
  名称：

  Spiro- and Dispiro-1,2-dioxolanes:  Contribution of Iron(II)-Mediated One-Electron vs Two-Electron Reduction to the Activity of Antimalarial Peroxides

  摘要：

  Fourteen spiro- and dispiro-1,2-dioxolanes were synthesized by peroxycarbenium ion annulations with alkenes in yields ranging from 30% to 94%. Peroxycarbenium ion precursors included triethylsilyldiperoxyketals and -acetals derived from geminal dihydroperoxides and from a new method employing triethylsilylperoxyketals and -acetals derived from ozonolysis of alkenes. The 1,2-dioxolanes were either inactive or orders of magnitude less potent than the corresponding 1,2,4-trioxolanes or artemisinin against P. falciparum in vitro and P. berghei in vivo. In reactions with iron(II), the predominant reaction course for 1,2-dioxolane 3a was two-electron reduction. In contrast, the corresponding 1,2,4-trioxolane 1 and the 1,2,4-trioxane artemisinin undergo primarily one-electron iron(II)-mediated reductions. The key structural element in the latter peroxides appears to be an oxygen atom attached to one or both of the peroxide-bearing carbon atoms that permits rapid beta-scission reactions (or H shifts) to form primary or secondary carbon-centered radicals rather than further reduction of the initially formed Fe(HI) complexed oxy radicals.

  DOI：

  10.1021/jm0707673
• 作为产物：
  描述：

  1,1-dihydroperoxy-4-phenylcyclohexane 、 三乙基硅基三氟甲磺酸酯 在 N-甲基咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以46%的产率得到4-phenyl-1,1-bis[(triethylsilyl)dioxy]cyclohexane
  参考文献：
  名称：

  Spiro- and Dispiro-1,2-dioxolanes:  Contribution of Iron(II)-Mediated One-Electron vs Two-Electron Reduction to the Activity of Antimalarial Peroxides

  摘要：

  Fourteen spiro- and dispiro-1,2-dioxolanes were synthesized by peroxycarbenium ion annulations with alkenes in yields ranging from 30% to 94%. Peroxycarbenium ion precursors included triethylsilyldiperoxyketals and -acetals derived from geminal dihydroperoxides and from a new method employing triethylsilylperoxyketals and -acetals derived from ozonolysis of alkenes. The 1,2-dioxolanes were either inactive or orders of magnitude less potent than the corresponding 1,2,4-trioxolanes or artemisinin against P. falciparum in vitro and P. berghei in vivo. In reactions with iron(II), the predominant reaction course for 1,2-dioxolane 3a was two-electron reduction. In contrast, the corresponding 1,2,4-trioxolane 1 and the 1,2,4-trioxane artemisinin undergo primarily one-electron iron(II)-mediated reductions. The key structural element in the latter peroxides appears to be an oxygen atom attached to one or both of the peroxide-bearing carbon atoms that permits rapid beta-scission reactions (or H shifts) to form primary or secondary carbon-centered radicals rather than further reduction of the initially formed Fe(HI) complexed oxy radicals.

  DOI：

  10.1021/jm0707673

文献信息

• Spiro- and Dispiro-1,2-dioxolanes:  Contribution of Iron(II)-Mediated One-Electron vs Two-Electron Reduction to the Activity of Antimalarial Peroxides
  作者：Xiaofang Wang、Yuxiang Dong、Sergio Wittlin、Darren Creek、Jacques Chollet、Susan A. Charman、Josefina Santo Tomas、Christian Scheurer、Christopher Snyder、Jonathan L. Vennerstrom

  DOI：10.1021/jm0707673

  日期：2007.11.1

  Fourteen spiro- and dispiro-1,2-dioxolanes were synthesized by peroxycarbenium ion annulations with alkenes in yields ranging from 30% to 94%. Peroxycarbenium ion precursors included triethylsilyldiperoxyketals and -acetals derived from geminal dihydroperoxides and from a new method employing triethylsilylperoxyketals and -acetals derived from ozonolysis of alkenes. The 1,2-dioxolanes were either inactive or orders of magnitude less potent than the corresponding 1,2,4-trioxolanes or artemisinin against P. falciparum in vitro and P. berghei in vivo. In reactions with iron(II), the predominant reaction course for 1,2-dioxolane 3a was two-electron reduction. In contrast, the corresponding 1,2,4-trioxolane 1 and the 1,2,4-trioxane artemisinin undergo primarily one-electron iron(II)-mediated reductions. The key structural element in the latter peroxides appears to be an oxygen atom attached to one or both of the peroxide-bearing carbon atoms that permits rapid beta-scission reactions (or H shifts) to form primary or secondary carbon-centered radicals rather than further reduction of the initially formed Fe(HI) complexed oxy radicals.