(2-allyloxyphenyl)trimethylsilane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (2-allyloxyphenyl)trimethylsilane
• 英文别名: Trimethyl-(2-prop-2-enoxyphenyl)silane；trimethyl-(2-prop-2-enoxyphenyl)silane
• 化学式: C₁₂H₁₈OSi
• 分子量: 206.36
• InChiKey: BUTDRWFXKOXHAF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  三氟甲磺酸酐 、 (2-allyloxyphenyl)trimethylsilane 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.66h， 以1.10 g的产率得到3-(allyloxy)-2-(trimethylsilyl)phenyl trifluoromethanesulfonate
  参考文献：
  名称：

  Synthesis of ortho-Haloaminoarenes by Aryne Insertion of Nitrogen–Halide Bonds

  摘要：

  A rapid and general access to ortho-haloaminoarenes has been developed by aryne insertion into N-chloramine, N-bromoamine, and N-iodoamine bonds via two complementary protocols harnessing fluoride-promoted 1,2-elimination of ortho-trimethylsilyl aryltriflates. Typically, electron-deficient N-chloramines effectively react with aryne intermediates generated at elevated temperature with CsF, while less stable N-haloamines are found more efficient under milder, TBAF-mediated aryne formation at room temperature. Both protocols demonstrate a good level of regioselectivity and functional group tolerance. Efforts to elucidate the mechanism of NX insertion are also discussed. The practical value of this transformation is highlighted by rapid synthesis of novel analogues of the antipsychotic cariprazine.

  DOI：

  10.1021/jo502541t
• 作为产物：
  描述：

  1-(allyloxy)-3-bromobenzene 、 六甲基二硅氮烷 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 (2-allyloxyphenyl)trimethylsilane
  参考文献：
  名称：

  Synthesis of ortho-Haloaminoarenes by Aryne Insertion of Nitrogen–Halide Bonds

  摘要：

  A rapid and general access to ortho-haloaminoarenes has been developed by aryne insertion into N-chloramine, N-bromoamine, and N-iodoamine bonds via two complementary protocols harnessing fluoride-promoted 1,2-elimination of ortho-trimethylsilyl aryltriflates. Typically, electron-deficient N-chloramines effectively react with aryne intermediates generated at elevated temperature with CsF, while less stable N-haloamines are found more efficient under milder, TBAF-mediated aryne formation at room temperature. Both protocols demonstrate a good level of regioselectivity and functional group tolerance. Efforts to elucidate the mechanism of NX insertion are also discussed. The practical value of this transformation is highlighted by rapid synthesis of novel analogues of the antipsychotic cariprazine.

  DOI：

  10.1021/jo502541t

文献信息

• Mechanistic studies on the reactions of trimethylsilanide and trimethylstannylide ions with haloarenes in hexamethylphosphoramide
  作者：Al Postigo、Santiago E. Vaillard、Roberto A. Rossi

  DOI：10.1016/s0022-328x(02)01572-3

  日期：2002.8

  former, compared with the more reactive, and less selective Me3Si− ions. When 1-allyloxy-2-halobenzenes (X=Cl, I) are allowed to react with Me3Sn− ions in HMPA, an ipso substitution product 6 is obtained, in addition to stannylated products on the allylic moiety. This reaction proceeds by a HME process, as opposed to the same reaction carried out in liquid ammonia, where (2,3-dihydro-benzofuran-3-yl

  大的正ρ选自Me得到的值3中号-离子与适当取代的氯代芳烃（4.1±0.1，以及对于M = Sn和硅分别2.94±0.02）可占强的负电荷的存在下反应取代反应的过渡态。这些ρ为我值3的Sn -和Me 3硅- ARX的亲核攻击为前者的总体更大的选择性提供的证据，与更具反应性，并且选择性较差我比较3硅-离子。当1-烯丙氧基-2-卤代苯（X = Cl，I）与Me 3 Sn反应-离子HMPA，一个本位取代产物6获得，除了stannylated产品上的烯丙基基团。与在液氨中进行的相同反应相反，该反应通过HME方法进行，其中通过S RN 1机理高产率地提供了（2,3-二氢-苯并呋喃-3-基甲基）-三甲基锡烷（4）。。我的反应3硅-与1-烯丙氧基-2-碘苯在HMPA，得到仅离子本位取代产物，即2-（烯丙氧基-苯基） -三甲基硅烷（11）中，通过高价的硅物种的中间性。
• Synthesis of <i>ortho</i>-Haloaminoarenes by Aryne Insertion of Nitrogen–Halide Bonds
  作者：Charles E. Hendrick、Qiu Wang

  DOI：10.1021/jo502541t

  日期：2015.1.16

  A rapid and general access to ortho-haloaminoarenes has been developed by aryne insertion into N-chloramine, N-bromoamine, and N-iodoamine bonds via two complementary protocols harnessing fluoride-promoted 1,2-elimination of ortho-trimethylsilyl aryltriflates. Typically, electron-deficient N-chloramines effectively react with aryne intermediates generated at elevated temperature with CsF, while less stable N-haloamines are found more efficient under milder, TBAF-mediated aryne formation at room temperature. Both protocols demonstrate a good level of regioselectivity and functional group tolerance. Efforts to elucidate the mechanism of NX insertion are also discussed. The practical value of this transformation is highlighted by rapid synthesis of novel analogues of the antipsychotic cariprazine.