1,1-bis[(triethylsilyl)dioxy]cyclohexane | 960121-23-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,1-bis[(triethylsilyl)dioxy]cyclohexane
• 英文别名: Triethyl-(1-triethylsilylperoxycyclohexyl)peroxysilane
• CAS: 960121-23-7
• 化学式: C₁₈H₄₀O₄Si₂
• 分子量: 376.684
• InChiKey: RSYMLYAXGGXFEU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.55
• 重原子数：
  24
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  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86%的产率得到14,15-Dioxadispiro[5.1.5.2]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：

  1,1-二氢过氧环己烷 、 三乙基硅基三氟甲磺酸酯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以18%的产率得到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

• Synthesis of Primary <i>gem</i>-Dihydroperoxides and Their Peroxycarbenium [3 + 2] Cycloaddition Reactions with Alkenes
  作者：Qinghong Zha、Yikang Wu

  DOI：10.1021/acs.joc.0c02180

  日期：2020.11.6

  a peroxycarbenium [3 + 2] cycloaddition reaction with alkenes for the first time. Aromatic substrates normally reacted smoothly, affording the expected 1,2-dioxolanes smoothly. Aliphatic aldehydes generally failed to yield 1,2-dioxolane. In all cases, unexpected formation of either a chlorohydrin or a 1,2-dichloride (with Cl atoms derived from TiCl4) depending on the alkene employed was observed, which

  众所周知，脂族醛的二氢过氧化非常困难，通常在羟基氢过氧化物阶段中途停止。现在已经研究了这种奇怪的现象，并且已经开发出一种高效的方案，用于将脂族醛转化为宝石-二氢过氧化物。使用2，6-二甲基吡啶作为碱，可以实现对初级宝石-二氢过氧化物的甲硅烷基保护，这也是由于未预期的碱诱导的分解而带来的挑战。甲硅烷基保护的宝石然后首次在过氧碳烯[3 + 2]环加成反应中与烯烃进行过-二氢过氧化物的检测。芳族底物通常反应平稳，平稳地提供了预期的1,2-二氧戊环。脂肪醛通常不能产生1，2-二氧戊环。在所有情况下，观察到取决于所使用的烯烃的意外形成氯醇或1,2-二氯化物（Cl原子源自TiCl 4），这显示了迄今为止未知的环加成反应方面，并有助于获得许多机理。见解。
• Probing the Peroxycarbenium [3+2] Cycloaddition Reactions with 1,2-Disubstituted Ethylenes: Results and Insights
  作者：Ze-Jun Xu、Sergio Wittlin、Yikang Wu

  DOI：10.1002/chem.201605871

  日期：2017.2.10

  the title reaction to be limited to only the alkenes with an unsubstituted terminal alkenic carbon were explored. In some “failed” cases the cycloaddition products actually formed but rearranged concurrently. An oxygen atom or a N‐Boc (Boc=tert‐butyloxycarbonyl) group at the double bond was proven essential for acquisition of intact [3+2] cycloaddition products from 1,2‐disubstituted ethylenes.

  探究了将标题反应限于仅具有未取代的末端烯基碳的烯烃的原因。在某些“失败”情况下，实际上形成了环加成产物，但同时发生了重排。事实证明，双键中的氧原子或N -Boc（Boc =叔-丁氧基羰基）基团对于从1,2-二取代的乙烯中获得完整的[3 + 2]环加成产物至关重要。
• Synthesis of spiro-1,2-dioxolanes and their activity against Plasmodium falciparum
  作者：Derek C. Martyn、Armando P. Ramirez、Meaghan J. Beattie、Joseph F. Cortese、Vishal Patel、Margaret A. Rush、K.A. Woerpel、Jon Clardy

  DOI：10.1016/j.bmcl.2008.10.083

  日期：2008.12

  Artemisinin-derived compounds play an integral role in current malaria chemotherapy. Given the virtual certainty of emerging resistance, we have investigated spiro-1,2-dioxolanes as an alternative scaffold. The endoperoxide functionality was generated by the SnCl(4)-mediated annulation of a bis-silylperoxide and an alkene. The first set of eight analogs gave EC(50) values of 50-150 nM against Plasmodium falciparum 3D7 and Dd2 strains, except for the carboxylic acid analog. A second series, synthesized by coupling a spiro-1,2-dioxolane carboxylic acid to four separate amines, afforded the most potent compound ( EC50 similar to 5 nM). (C) 2008 Elsevier Ltd. All rights reserved.
• 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.