(1-Methyl-2-trimethylsilanyl-ethyl)-triphenyl-phosphonium; iodide | 72385-60-5

• 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: (1-Methyl-2-trimethylsilanyl-ethyl)-triphenyl-phosphonium; iodide
• CAS: 72385-60-5
• 化学式: C₂₄H₃₀PSi*I
• 分子量: 504.466
• InChiKey: NKQVQUKILMBEEH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.71
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (1-Methyl-2-trimethylsilanyl-ethyl)-triphenyl-phosphonium; iodide 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 20.67h， 生成 3,3,6-trimethyl-7-trimethylsilylhept-5-enal
  参考文献：
  名称：

  Intramolecular Anodic Olefin Coupling Reactions: A New Approach to the Synthesis of Angularly Fused, Tricyclic Enones

  摘要：

  A number of intramolecular anodic olefin coupling reactions have been examined in order to determine the feasibility of using a sequential electrochemical oxidation-aldol condensation approach for constructing polycyclic enones. Initially, substrates comprised of an aldehyde enol ether tethered to a ketone enol ether were examined. In a model study, it was shown that such a substrate could lead to a successful electrochemical oxidation-aldol condensation sequence. However, the difficulties associated with both the synthesis and the poor stability of the ketone enol ethers greatly reduced the potential utility of this approach. This problem was circumvented by taking advantage of the compatibility of allylsilane groups with the electrolysis reaction. In these examples, ozonolysis of the electrochemical cyclization product afforded the 1,4-dicarbonyl substrate needed for the aldol condensation. The use of the less reactive allylsilane group in the electrochemical reaction still allowed for the construction of quaternary carbons. Finally a pair of angularly fused, tricyclic enones were synthesized. The regiochemistry of the enone in the product could be controlled by the proper choice of the substrate for the electrolysis and manipulation of the resulting cyclized product.

  DOI：

  10.1021/jo00088a019
• 作为产物：
  描述：

  碘甲基三甲基硅烷 、 乙基三苯基溴化膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 (1-Methyl-2-trimethylsilanyl-ethyl)-triphenyl-phosphonium; iodide
  参考文献：
  名称：

  Intramolecular Anodic Olefin Coupling Reactions: A New Approach to the Synthesis of Angularly Fused, Tricyclic Enones

  摘要：

  A number of intramolecular anodic olefin coupling reactions have been examined in order to determine the feasibility of using a sequential electrochemical oxidation-aldol condensation approach for constructing polycyclic enones. Initially, substrates comprised of an aldehyde enol ether tethered to a ketone enol ether were examined. In a model study, it was shown that such a substrate could lead to a successful electrochemical oxidation-aldol condensation sequence. However, the difficulties associated with both the synthesis and the poor stability of the ketone enol ethers greatly reduced the potential utility of this approach. This problem was circumvented by taking advantage of the compatibility of allylsilane groups with the electrolysis reaction. In these examples, ozonolysis of the electrochemical cyclization product afforded the 1,4-dicarbonyl substrate needed for the aldol condensation. The use of the less reactive allylsilane group in the electrochemical reaction still allowed for the construction of quaternary carbons. Finally a pair of angularly fused, tricyclic enones were synthesized. The regiochemistry of the enone in the product could be controlled by the proper choice of the substrate for the electrolysis and manipulation of the resulting cyclized product.

  DOI：

  10.1021/jo00088a019

文献信息

• The wittig synthesis of allylic organosilicon compounds
  作者：Dietmar Seyferth、Karl R. Wursthorn、Thomas F.O. Lim、Dennis J. Sepelak

  DOI：10.1016/s0022-328x(00)82823-5

  日期：1979.11

  henylphosphoranes (prepared by the action of alkylidenetriphenylphosphoranes on iodomethylsilicon compounds, followed by deprotonation of the resulting β-silylalkyltriphenylphosphonium iodides) with aldehydes and ketones provide a useful route to allylic silicon compounds. The β-silyl Wittig reagents prepared and utilized in this study include Pha3P=CHCH2SiMe3, Ph3P=C(CH3)CH2,SiMe3, Ph3P=C(C6H5)CH2SiMe3

  β-甲硅烷基烷基亚甲基三苯基phenyl膦与醛和酮的反应（通过烷基亚甲基三苯基膦对碘甲基硅化合物的作用制备，然后使所得的β-甲硅烷基烷基三苯基phOSph碘化物去质子化）为制备烯丙基硅化合物提供了一条有用的途径。本研究中制备和使用的β-甲硅烷基Wittig试剂包括Pha 3 P = CHCH 2 SiMe 3，Ph 3 P = C（CH 3）CH 2，SiMe 3，Ph 3 P = C（C 6 H 5）CH 2 SiMe 3，Ph 3 P = CHCH 2 SiMe 2H，Ph 3 P ＝ CHCH 2 SiMe 2 OSiMe 3和Ph 3 P ＝ CHCH 2 SiMe-（OSiMe 3）2。
• The synthesis of 3,3-difluoroallyl derivatives of silicon by an organophosphorus route
  作者：Dietmar Seyferth、Karl R. Wursthorn、Thomas F.O. Lim、Dennis J. Sepelak

  DOI：10.1016/s0022-328x(00)82432-8

  日期：1981.2