1,1-di(triethylsilyldioxy)-4-tert-butylcyclohexane | 960121-25-9

• 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-di(triethylsilyldioxy)-4-tert-butylcyclohexane
• 英文别名: 4-tert-Butylcyclohexanone bis(triethylsilylperoxy) ketal；(4-tert-butyl-1-triethylsilylperoxycyclohexyl)peroxy-triethylsilane
• CAS: 960121-25-9
• 化学式: C₂₂H₄₈O₄Si₂
• 分子量: 432.792
• InChiKey: ORTIQQUDDIHPQO-UHFFFAOYSA-N

物化性质

• 沸点：
  403.7±15.0 °C(Predicted)
• 密度：
  0.92±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.83
• 重原子数：
  28
• 可旋转键数：
  13
• 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-di(triethylsilyldioxy)-4-tert-butylcyclohexane 在 四丁基氟化铵 、 四氯化锡 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 22.5h， 生成 (8-tert-butyl-1,2-dioxaspiro[4.5]dec-3-yl)-methanol
  参考文献：
  名称：

  Synthesis of 1,2-Dioxolanes by Annulation Reactions of Peroxycarbenium Ions with Alkenes

  摘要：

  The annulation reactions of alkenes with peroxycarbenium ions enable the synthesis of a variety of functionalizable 1,2-dioxolanes. Triethysilyl-protected peroxycarbenium ions proved to be optimal for the annulation reaction. Using this method, plakinic acid analogues can be synthesized in three steps from the corresponding ketone and alkene.

  DOI：

  10.1021/ol051703u
• 作为产物：
  描述：

  4-叔丁基环己酮 在 双氧水 、 rhenium(VII) oxide 、 三乙胺 作用下， 以 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 1.0h， 生成 1,1-di(triethylsilyldioxy)-4-tert-butylcyclohexane
  参考文献：
  名称：

  从单活化 1,1-二氢过氧化物的断裂中产生单线态氧

  摘要：

  分子氧 ( 1 O 2 )的第一个单线激发态是化学、生物学和医学中的重要氧化剂。1 O 2最常通过基态氧的光敏激发产生。1 O 2也可以通过过氧化氢和其他过氧化物的分解化学生成。然而，大多数这些“暗氧化”需要与短1 O 2相关的富水介质寿命，并且需要能够在有机溶剂中进行氧化。我们现在报告 1,1-二氢过氧化物的单活化衍生物经历了以前未观察到的碎裂，以产生高产率的单线态分子氧 ( 1 O 2 )。可以在多种有机溶剂中进行的断裂需要过氧阴离子和被激活以进行异裂裂解的过氧化物之间存在孪生关系。该反应适用于一系列骨架和活化基团，通过原位活化，可直接应用于 1,1-二氢过氧化物。我们的调查表明，碎裂涉及过氧阴离子的限速形成，过氧阴离子通过类似 Grob 的过程分解。

  DOI：

  10.1021/jo202265j

文献信息

• 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.
• Generation of Singlet Oxygen from Fragmentation of Monoactivated 1,1-Dihydroperoxides
  作者：Jiliang Hang、Prasanta Ghorai、Solaire A. Finkenstaedt-Quinn、Ilhan Findik、Emily Sliz、Keith T. Kuwata、Patrick H. Dussault

  DOI：10.1021/jo202265j

  日期：2012.2.3

  short 1O2 lifetimes, and there is a need for oxygenations able to be conducted in organic solvents. We now report that monoactivated derivatives of 1,1-dihydroperoxides undergo a previously unobserved fragmentation to generate high yields of singlet molecular oxygen (1O2). The fragmentations, which can be conducted in a variety of organic solvents, require a geminal relationship between a peroxyanion and

  分子氧 ( 1 O 2 )的第一个单线激发态是化学、生物学和医学中的重要氧化剂。1 O 2最常通过基态氧的光敏激发产生。1 O 2也可以通过过氧化氢和其他过氧化物的分解化学生成。然而，大多数这些“暗氧化”需要与短1 O 2相关的富水介质寿命，并且需要能够在有机溶剂中进行氧化。我们现在报告 1,1-二氢过氧化物的单活化衍生物经历了以前未观察到的碎裂，以产生高产率的单线态分子氧 ( 1 O 2 )。可以在多种有机溶剂中进行的断裂需要过氧阴离子和被激活以进行异裂裂解的过氧化物之间存在孪生关系。该反应适用于一系列骨架和活化基团，通过原位活化，可直接应用于 1,1-二氢过氧化物。我们的调查表明，碎裂涉及过氧阴离子的限速形成，过氧阴离子通过类似 Grob 的过程分解。
• Synthesis of 1,2-Dioxolanes by Annulation Reactions of Peroxycarbenium Ions with Alkenes
  作者：Armando Ramirez、K. A. Woerpel

  DOI：10.1021/ol051703u

  日期：2005.10.1

  The annulation reactions of alkenes with peroxycarbenium ions enable the synthesis of a variety of functionalizable 1,2-dioxolanes. Triethysilyl-protected peroxycarbenium ions proved to be optimal for the annulation reaction. Using this method, plakinic acid analogues can be synthesized in three steps from the corresponding ketone and alkene.