trimethyl<(4-phenyl-1-cyclohexen-1-yl)ethynyl>silane

• 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: trimethyl<(4-phenyl-1-cyclohexen-1-yl)ethynyl>silane
• 英文别名: Trimethyl-[2-(4-phenylcyclohexen-1-yl)ethynyl]silane
• 化学式: C₁₇H₂₂Si
• 分子量: 254.447
• InChiKey: MBJPAEDLNKXGQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.76
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  4-苯基环己酮 在 bis-triphenylphosphine-palladium(II) chloride 三乙胺 、 lithium diisopropyl amide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 trimethyl<(4-phenyl-1-cyclohexen-1-yl)ethynyl>silane
  参考文献：
  名称：

  Generation of Cycloalkylidene Carbenes via Exo-Type Cyclization of Alkynyllithiums Bearing Remote Leaving Group

  摘要：

  The reaction of 5-hexynyl tosylate (3a) with alkynyllithium (RC=CLi; R Ph, TMS) gives enynes 5 and 6. The reaction proceeds through a mechanism involving a novel exo-type cyclization of 6-lithiod-hexynyl tosylate to form cyclopentylidene carbene. Enyne 6 is produced by the addition of RC=CLi to the carbene, whereas rearrangement of the carbene to cyclohexyne followed by carbolithiation with RC=CLi gives enyne 5. The formation of cyclopentylidene carbene and cyclohexyne as intermediates is clearly demonstrated by trapping experiments with cyclohexene land triethylsilane) and with 1,3-diphenylisobenzofuran, respectively. Alkynyllithiums derived from 3-butynyl and 6-heptynyl p-fluorobenzenesulfonates (19a,b) undergo a similar exo-type cyclization to give cyclopropylidene and cyclohexylidene carbenes, respectively.

  DOI：

  10.1021/jo981411p

文献信息

• Formal Synthesis of <scp>d</scp>-<i>myo</i>-Inositol 1,4,5-Tris(dihydrogen phosphate):  Cyclization by an Unusual Ene Reaction and Use of the Bu₂SnCl₂/Bu₂SnH₂ Reagent for Generating an Equatorial Alcohol
  作者：Derrick L. J. Clive、Xiao He、Maarten H. D. Postema、M. Jeffrey Mashimbye

  DOI：10.1021/jo990086i

  日期：1999.6.1

  D-Glucose was converted into the propargyl silane aldehyde 5, which, on treatment with camphorsulfonic acid, cyclized with retention of silicon. The allenic product (7) was elaborated via ketone 24 into 4, which had previously been converted into D-myo-inositol 1,4,5-tris(dihydrogen phosphate). Selective reduction of the advanced intermediate 24 was accomplished with Bu2SnCl2/Bu2SnH2, a reagent mixture that shows a very strong preference for generating equatorial alcohols. The cyclization step leading to allene 7 was studied by examining a number of model compounds; the unusual retention of silicon appears to be limited to highly oxygenated substrates, such as 5 and its all-benzyl analogue (27).
• Generation of Cycloalkylidene Carbenes via Exo-Type Cyclization of Alkynyllithiums Bearing Remote Leaving Group
  作者：Toshiro Harada、Katsuhiro Iwazaki、Takeshi Otani、Akira Oku

  DOI：10.1021/jo981411p

  日期：1998.11.1

  The reaction of 5-hexynyl tosylate (3a) with alkynyllithium (RC=CLi; R Ph, TMS) gives enynes 5 and 6. The reaction proceeds through a mechanism involving a novel exo-type cyclization of 6-lithiod-hexynyl tosylate to form cyclopentylidene carbene. Enyne 6 is produced by the addition of RC=CLi to the carbene, whereas rearrangement of the carbene to cyclohexyne followed by carbolithiation with RC=CLi gives enyne 5. The formation of cyclopentylidene carbene and cyclohexyne as intermediates is clearly demonstrated by trapping experiments with cyclohexene land triethylsilane) and with 1,3-diphenylisobenzofuran, respectively. Alkynyllithiums derived from 3-butynyl and 6-heptynyl p-fluorobenzenesulfonates (19a,b) undergo a similar exo-type cyclization to give cyclopropylidene and cyclohexylidene carbenes, respectively.