2-[3-[Dimethyl(phenyl)silyl]propyl]cyclohexan-1-one

• 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-[3-[Dimethyl(phenyl)silyl]propyl]cyclohexan-1-one
• 化学式: C₁₇H₂₆OSi
• 分子量: 274.478
• InChiKey: KWJRXDXBJKOKKZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.14
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-[3-[Dimethyl(phenyl)silyl]propyl]cyclohexan-1-one 在 tetrafluoroboric acid 、 三乙胺 、 间氯过氧苯甲酸 作用下， 生成 2-(γ-Hydroxypropyl)-cyclohexanon
  参考文献：
  名称：

  Silicon-Promoted Carbon-Carbon Bond Formation between Ketones and Allyl- or Vinylsilanes Catalyzed by Manganese(IV) Dioxide

  摘要：

  The influence of silicon on the carbon-carbon bond formation was investigated by use of various silylalkenes to react with ketones. Treatment of an allylsilane (CH2=CHCH(2)SiMe(m)Ph(n); m + n 3) with various ketones (20 equiv) in the presence of MnO2 (2.0 equiv) and a drop of acetic acid at 140 degrees C in a sealed tube produced the corresponding hydrogen atom transfer adducts in 54-85% yields. Performance of the same reactions by replacement of the allylsilane with a vinylsilane (i.e., CH2=CHSiMe(3) and CH2=CHSiMeEt(2)) afforded adducts in 59-75% yields. Furthermore, reaction of diallyldimethylsilane with acetone or 3-methyl-2-butanone under the same conditions afforded 4-(3,3-dimethyl-3-silacyclohexyl)butan-2-one (81%) and 4-(3,3-dimethyl-3-silacyclohexyl)-3,3-dimethylbutan-2-one (65%), respectively. The results indicate that the alpha- and the beta-electronic effects of a silicon atom promoted the C-C bond formation, while the regioselectivity came from the steric effect of the silyl group.

  DOI：

  10.1021/jo00113a027
• 作为产物：
  描述：

  2-烯丙基环己酮 、 二甲基苯基硅烷 在 (bis(diisopropylphenyl-imidazol-2-ylidene)phenyl)CoN₂ 作用下， 以 苯 为溶剂， 反应 2.5h， 以94%的产率得到2-[3-[Dimethyl(phenyl)silyl]propyl]cyclohexan-1-one
  参考文献：
  名称：

  使用叔硅烷和氢硅氧烷对烯烃进行氢化硅烷化的高化学选择性钴催化剂

  摘要：

  带有附加功能的烯烃底物的氢化硅烷化难以使用富含地球的催化剂来实现，并且还没有被富含地球的过渡金属和叔硅烷或氢硅氧烷广泛地实现。本文报道的是定义明确的双（卡宾）钴（I）-二氮配合物，用于末端烯烃的高效，催化抗马尔科夫尼科夫氢化硅烷化反应，具有广泛的底物范围。含有羟基，氨基，酯，环氧化物，酮，甲酰基和腈基的烯烃按该反应顺序被选择性地氢化硅烷化。反应性中间体的多核NMR研究提供了对该机理的见解。

  DOI：

  10.1021/acscatal.6b01091

文献信息

• Electronic and steric effects of various silyl groups in radical addition reactions
  作者：Jih Ru Hwu、Ke Yung King、I-Fay Wu、Gholam H. Hakimelahi

  DOI：10.1016/s0040-4039(98)00569-3

  日期：1998.5

  The ligands on a silicon atom in allylsilanes were found to influence the efficiency of their reaction with ketones in the presence of MnO2. An electron-donating group on silicon provided a promoting effect, yet the steric effect of a bulky silyl group retarded the addition process.

  发现烯丙基硅烷中硅原子上的配体会影响它们在MnO 2存在下与酮的反应效率。硅上的给电子基团提供了促进作用，而庞大的甲硅烷基的空间效应却阻碍了加成过程。
• A Highly Chemoselective Cobalt Catalyst for the Hydrosilylation of Alkenes using Tertiary Silanes and Hydrosiloxanes
  作者：Abdulrahman D. Ibrahim、Steven W. Entsminger、Lingyang Zhu、Alison R. Fout

  DOI：10.1021/acscatal.6b01091

  日期：2016.6.3

  The hydrosilylation of alkene substrates bearing additional functionalities is difficult to achieve using earth-abundant catalysts and has not been extensively realized with both earth-abundant transition metals and tertiary silanes or hydrosiloxanes. Reported herein is a well-defined bis(carbene) cobalt(I)-dinitrogen complex for the efficient, catalytic anti-Markovnikov hydrosilylation of terminal

  带有附加功能的烯烃底物的氢化硅烷化难以使用富含地球的催化剂来实现，并且还没有被富含地球的过渡金属和叔硅烷或氢硅氧烷广泛地实现。本文报道的是定义明确的双（卡宾）钴（I）-二氮配合物，用于末端烯烃的高效，催化抗马尔科夫尼科夫氢化硅烷化反应，具有广泛的底物范围。含有羟基，氨基，酯，环氧化物，酮，甲酰基和腈基的烯烃按该反应顺序被选择性地氢化硅烷化。反应性中间体的多核NMR研究提供了对该机理的见解。
• Silicon-Promoted Carbon-Carbon Bond Formation between Ketones and Allyl- or Vinylsilanes Catalyzed by Manganese(IV) Dioxide
  作者：Jih Ru Hwu、Buh-Luen Chen、Shui-Sheng Shiao

  DOI：10.1021/jo00113a027

  日期：1995.4

  The influence of silicon on the carbon-carbon bond formation was investigated by use of various silylalkenes to react with ketones. Treatment of an allylsilane (CH2=CHCH(2)SiMe(m)Ph(n); m + n 3) with various ketones (20 equiv) in the presence of MnO2 (2.0 equiv) and a drop of acetic acid at 140 degrees C in a sealed tube produced the corresponding hydrogen atom transfer adducts in 54-85% yields. Performance of the same reactions by replacement of the allylsilane with a vinylsilane (i.e., CH2=CHSiMe(3) and CH2=CHSiMeEt(2)) afforded adducts in 59-75% yields. Furthermore, reaction of diallyldimethylsilane with acetone or 3-methyl-2-butanone under the same conditions afforded 4-(3,3-dimethyl-3-silacyclohexyl)butan-2-one (81%) and 4-(3,3-dimethyl-3-silacyclohexyl)-3,3-dimethylbutan-2-one (65%), respectively. The results indicate that the alpha- and the beta-electronic effects of a silicon atom promoted the C-C bond formation, while the regioselectivity came from the steric effect of the silyl group.