[3,5-bis(trifluoromethyl)phenyl]triethylsilane

• 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: [3,5-bis(trifluoromethyl)phenyl]triethylsilane
• 英文别名: 3,5-Bis(trifluoromethyl)phenyltriethylsilane；[3,5-bis(trifluoromethyl)phenyl]-triethylsilane
• 化学式: C₁₄H₁₈F₆Si
• 分子量: 328.373
• InChiKey: AYYRTMJPPLFBQW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.44
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [3,5-bis(trifluoromethyl)phenyl]triethylsilane 在 4-碘苯甲醚 、 加尔万氧基自由基 、 cesium fluoride 、 copper(ll) bromide 、 2-二苯基磷-2'-(N,N-二甲氨基)联苯 作用下， 反应 24.0h， 以16%的产率得到间二三氟甲苯
  参考文献：
  名称：

  铜（II）催化的交叉偶联反应合成联芳基和三芳基的芳基（三乙基）硅烷

  摘要：

  发现在催化量的CuBr 2和Ph-Davephos以及氟化铯作为化学计量的碱存在下，芳基（三乙基）硅烷与碘代芳烃发生交叉偶联。由于硅试剂可通过芳族底物的催化CH甲硅烷基化而容易获得，因此净转化可通过三乙基甲硅烷基化将芳族烃与碘代芳烃偶联。

  DOI：

  10.1002/anie.201608667
• 作为产物：
  描述：

  三乙基硅烷 、 间二三氟甲苯 在 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 3,3-二甲基-1-丁烯 、 3,4,7,8-四甲基-1,10-菲罗啉 作用下， 以 环己烷 为溶剂， 反应 4.0h， 以98%的产率得到[3,5-bis(trifluoromethyl)phenyl]triethylsilane
  参考文献：
  名称：

  无方向基的铱催化多环芳族化合物的分子间脱氢甲硅烷基化

  摘要：

  这项研究描述了铱催化的无环基团的多环芳族化合物的C（sp 2）H键的分子间脱氢甲硅烷基化反应。该反应通过两个硅产生的各种芳基硅烷 H和13 C  H键活化，用氢作为唯一的副产物。反应性受芳香族化合物电子性质的影响，缺电子和多环芳香族化合物的甲硅烷基化反应有效进行。位点选择性主要受空间因素控制。因此，与芳香族化合物的一般亲电官能化所观察到的相比，当前的官能化以相反的化学选择性和位点选择性进行。

  DOI：

  10.1002/chem.201406508

文献信息

• Iridium-Catalyzed Intermolecular Dehydrogenative Silylation of Polycyclic Aromatic Compounds without Directing Groups
  作者：Masahito Murai、Keishi Takami、Kazuhiko Takai

  DOI：10.1002/chem.201406508

  日期：2015.3.16

  iridium‐catalyzed intermolecular dehydrogenative silylation of C(sp2)H bonds of polycyclic aromatic compounds without directing groups. The reaction produced various arylsilanes through both SiH and CH bond activation, with hydrogen as the sole byproduct. Reactivity was affected by the electronic nature of the aromatic compounds, and silylation of electron‐deficient and polycyclic aromatic compounds proceeded

  这项研究描述了铱催化的无环基团的多环芳族化合物的C（sp 2）H键的分子间脱氢甲硅烷基化反应。该反应通过两个硅产生的各种芳基硅烷 H和13 C  H键活化，用氢作为唯一的副产物。反应性受芳香族化合物电子性质的影响，缺电子和多环芳香族化合物的甲硅烷基化反应有效进行。位点选择性主要受空间因素控制。因此，与芳香族化合物的一般亲电官能化所观察到的相比，当前的官能化以相反的化学选择性和位点选择性进行。
• Intermolecular and Intramolecular, Platinum-Catalyzed, Acceptorless Dehydrogenative Coupling of Hydrosilanes with Aryl and Aliphatic Methyl C−H Bonds
  作者：Naofumi Tsukada、John F. Hartwig

  DOI：10.1021/ja050612p

  日期：2005.4.1

  Intermolecular acceptorless dehydrogenative coupling of silanes with arene C-H bonds and intramolecular coupling of silanes with aryl and alkyl C-H bonds occur in good yield in the presence of 5 mol % of TpMe2PtMe2H (TpMe2 = hydridotris(3,5-dimethylpyrazolyl)borate) and related platinum(IV) complexes. The intermolecular reactions of arenes occurred with both trialkyl and dialkylaryl silanes. Intramolecular reactions of dialkylsilylalkylarenes occurred at aryl C-H bonds, and reactions of tributylsilane or dibutylphenylsilane occurred intramolecularly at the aliphatic, primary C-H bond. The reactions of arenes occurred preferentially at the least sterically hindered C-H bonds and preferentially with more electron-poor arenes. Crossover experiments and the lack of reactivity of the arylsilanes with H2 imply that the dehydrogenative silylation of arenes can be irreversible, even in a closed reaction vessel.
• Aryl(triethyl)silanes for Biaryl and Teraryl Synthesis by Copper(II)-Catalyzed Cross-Coupling Reaction
  作者：Takeshi Komiyama、Yasunori Minami、Tamejiro Hiyama

  DOI：10.1002/anie.201608667

  日期：2016.12.19

  Aryl(triethyl)silanes are found to undergo cross‐coupling with iodoarenes in the presence of catalytic amounts of CuBr2 and Ph‐Davephos, as well as cesium fluoride as a stoichiometric base. Because the silicon reagents are readily accessible through catalytic C−H silylation of aromatic substrates, the net transformation allows coupling of aromatic hydrocarbons with iodoarenes via triethylsilylation

  发现在催化量的CuBr 2和Ph-Davephos以及氟化铯作为化学计量的碱存在下，芳基（三乙基）硅烷与碘代芳烃发生交叉偶联。由于硅试剂可通过芳族底物的催化CH甲硅烷基化而容易获得，因此净转化可通过三乙基甲硅烷基化将芳族烃与碘代芳烃偶联。
• Intermolecular C–H Silylation of Arenes and Heteroarenes with HSiEt₃under Operationally Diverse Conditions: Neat/Stoichiometric and Acceptor/Acceptorless
  作者：Kang-sang Lee、Dimitris Katsoulis、Jongwook Choi

  DOI：10.1021/acscatal.5b02806

  日期：2016.3.4

  Efficient protocols for Rh-catalyzed intermolecular C-H silylation of unactivated arenes and heteroarenes are disclosed. The silylations are catalyzed by a Rh-complex (2 mol %) derived in situ from commercially available Rh(nbd)(2)BF4 and (S,S)-i-Pr-BPE (L3) with Et3SiH in the presence of hydrogen acceptor under either neat (excess of arene) or stoichiometric conditions. The regioselectivity is determined mainly by the steric bulk of the substituents and by the electronic effect as an ancillary factor. In addition, our preliminary result shows that the current protocol catalyzes the silylation of arenes in the absence of hydrogen acceptors.