2-(trimethylsilyl)-2-cyclohexenyl hydroperoxide | 143100-83-8

• 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: 2-(trimethylsilyl)-2-cyclohexenyl hydroperoxide
• 英文别名: (6-Hydroperoxycyclohexen-1-yl)-trimethylsilane
• CAS: 143100-83-8
• 化学式: C₉H₁₈O₂Si
• 分子量: 186.326
• InChiKey: KHRGALKGTOFJGR-UHFFFAOYSA-N

物化性质

• 沸点：
  235.6±40.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.83
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)-2-cyclohexenyl hydroperoxide 在 NaOH buffer 、 seleno-subtilisin Carlsberg 、 硫代硝基苯甲酸 、 柠檬酸 作用下， 以 乙醇 、 水 为溶剂， 反应 0.22h， 生成 2-(三甲基甲硅烷基)环己-2-烯-1-醇
  参考文献：
  名称：

  不对称合成中的半合成酶：硒代-枯草杆菌蛋白酶催化的外消旋氢过氧化物的对映选择性还原。

  摘要：

  将丝氨酸蛋白酶枯草杆菌蛋白酶化学转化为过氧化物酶活性的硒代枯草杆菌蛋白酶。在硫酚的存在下，这种半合成酶催化外消旋氢过氧化物的对映选择性还原，从而以半制备规模生产旋光性氢过氧化物和醇。测定了动力学参数和硒代枯草杆菌蛋白酶催化的各种手性氢过氧化物还原的对映选择性。该半合成酶的催化效率与天然辣根过氧化物酶的催化效率相当。硒代枯草杆菌蛋白酶的对映选择性与先前用于旋光活性氢过氧化物合成的天然酶相反。所以，

  DOI：

  10.1021/jo981665a
• 作为产物：
  描述：

  1-环己烯-1-基(三甲基)硅烷 以45%的产率得到
  参考文献：
  名称：

  Adam Waldemar, Richter Markus J., J. Org. Chem., 59 (1994) N 12, S 3335- 3340

  摘要：

  DOI：

文献信息

• Highly regio - and diastereoselective synthesis of epoxy alcohols directly from vinyl silanes by photo-oxygenation and titanium-catalyzed oxygen transfer
  作者：Waldemar Adam、Markus Richter

  DOI：10.1016/s0040-4039(00)92663-7

  日期：1992.6

  The photooxygenation of vinyl silanes 1 in the presence of Ti(OiPr)4 afforded
• Regioselectivity of the Singlet Oxygen Ene Reaction (Schenck Reaction) with Vinylsilanes
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1021/jo00091a020

  日期：1994.6

  The ene reaction-of singlet oxygen and vinylsilanes 1 with various substitution patterns and double-bond geometry has been studied. beta-Silyl allylic hydroperoxides 2 were the major products of the photooxygenation, accompanied by smaller amounts of alpha,beta-unsaturated ketones 3. The latter derive from decomposition of the regioisomeric alpha-hydroperoxy silanes 4 by elimination of silanol. Regioselectivities up to 97:3 were observed for vinylsilanes with a methyl group geminal to the silyl group and with cyclic derivatives. Z-Configurated substrates showed lower regioselectivity and reactivity. Elongation of the carbon chain at the geminal position also increased the amount enone formed. These results are rationalized in terms of stereoelectronic effects imposed by the silyl group on the ring-opening of the perepoxide intermediate.
• Extension of the Criegee Rearrangement: Synthesis of Enol Ethers from Secondary Allylic Hydroperoxides
  作者：Richard M. Goodman、Yoshito Kishi

  DOI：10.1021/jo00097a006

  日期：1994.9

  The Criegee rearrangement has been extended to secondary allylic hydroperoxides, allowing for the selective synthesis of cyclic and acyclic enol ethers; the effect of base and electrophilic agent was studied.
• Biocatalytic kinetic resolution of hydroperoxy vinylsilanes by horseradish peroxidase (HRP) and lipases, a comparative study
  作者：Waldemar Adam、Cordula Mock-Knoblauch、Chantu R. Saha-Möller

  DOI：10.1016/s0957-4166(97)00197-3

  日期：1997.6

  The kinetic resolution of hydroperoxy vinylsilanes 1 has been investigated by the horseradish-peroxidase(HRP)-catalyzed reduction with guaiacol and by the acetylation with isopropenyl acetate in the presence of various lipases. The best results (ee values up to 89% at 48% conversion) were obtained for the lipase-catalyzed reactions. (C) 1997 Elsevier Science Ltd.