4-(triethylsilyl)benzonitrile | 882049-63-0

• 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: 4-(triethylsilyl)benzonitrile
• 英文别名: 4-Triethylsilylbenzonitrile
• CAS: 882049-63-0
• 化学式: C₁₃H₁₉NSi
• 分子量: 217.386
• InChiKey: PMWDRKXNNOTENL-UHFFFAOYSA-N

物化性质

• 沸点：
  299.0±13.0 °C(Predicted)
• 密度：
  0.92±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.27
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(triethylsilyl)benzonitrile 、 六甲基二硅烷 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 作用下， 以 乙基环己烷 为溶剂， 反应 15.0h， 以74%的产率得到triethyl(4-(trimethylsilyl)phenyl)silane
  参考文献：
  名称：

  Rhodium-Catalyzed Silylation and Intramolecular Arylation of Nitriles via the Silicon-Assisted Cleavage of Carbon−Cyano Bonds

  摘要：

  A rhodium-catalyzed silylation reaction of carbon-cyano bonds using disilane has been developed. Under these catalytic conditions, carbon-cyano bonds in aryl, alkenyl, allyl, and benzyl cyanides bearing a variety of functional groups can be silylated. The observation of an enamine side product in the silylation of benzyl cyanides and related stoichiometric studies indicate that the carbon-cyano bond cleavage proceeds through the deinsertion of silyl isocyanide from eta(2)-iminoacyl complex B. Knowledge gained from these studies has led to the development of a new intramolecular biaryl coupling reaction in which aryl cyanides and aryl chlorides are cross-coupled.

  DOI：

  10.1021/ja804992n
• 作为产物：
  描述：

  三乙基硅烷 、 4-碘氰基苯 在 N,N-二异丙基乙胺 作用下， 以 N-甲基吡咯烷酮 为溶剂， 反应 15.0h， 以74%的产率得到4-(triethylsilyl)benzonitrile
  参考文献：
  名称：

  使用可磁循环使用的双金属Pd–Pt–Fe 3 O 4催化剂对卤代芳基进行芳基硅烷化†

  摘要：

  过渡金属催化的甲硅烷基化通常涉及均相不可回收的催化体系的使用。在这项工作中，已经报道了合成芳基硅烷的可回收催化体系的第一个实例，该体系利用了双金属配合物Pd–Pt–Fe 3 O 4纳米颗粒。通过使芳基碘化物（或溴化物）与氢化硅烷反应来制备各种芳基硅烷。该方法显示出对酯，酮，醛，硝基和氰基的良好官能团耐受性。双金属Pd–Pt–Fe 3 O 4催化体系的活性优于单金属Pt–Fe 3 O 4和Pd–Fe 3 O 4。催化剂。此外，双金属Pd–Pt–Fe 3 O 4催化体系可以轻松回收并重复使用超过20个循环。

  DOI：

  10.1039/c7cc09926f

文献信息

• 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。
• Silylation of Aryl Chlorides by Bimetallic Catalysis of Palladium and Gold on Alloy Nanoparticles
  作者：Hiroki Miura、Yosuke Masaki、Yohei Fukuta、Tetsuya Shishido

  DOI：10.1002/adsc.202000045

  日期：2020.7.16

  Supported palladium‐gold alloy‐catalyzed cross‐coupling of aryl chlorides and hydrosilanes enabled the selective formation of aryl‐silicon bonds. Whereas a monometallic palladium catalyst predominantly promoted the hydrodechlorination of aryl chlorides and gold nanoparticles showed no catalytic activity, gold‐rich palladium‐gold alloy nanoparticles efficiently catalyzed the title reaction to give arylsilanes

  受支撑的钯金合金催化的芳基氯和氢硅烷的交叉偶联使得能够选择性地形成芳基-硅键。单金属钯催化剂主要促进芳基氯化物的加氢脱氯作用，而金纳米颗粒没有催化活性，而富金的钯金合金纳米颗粒则有效地催化了标题反应，从而提供了高选择性的芳基硅烷。各种各样的芳基氯和氢硅烷参与了非均相催化反应，以34–80％的收率提供了相应的芳基硅烷。详尽的机理研究表明，合金纳米粒子表面上的钯和金原子分别独立地充当形成芳基亲核试剂和甲硅烷基亲电试剂的活性位点，
• Palladium-Catalyzed Silylation of Electron-Deficient Aryl Iodides Using Triorganosilane in the Presence of Pyridine and LiCl
  作者：Muneaki Iizuka、Yoshinori Kondo

  DOI：10.1002/ejoc.200701141

  日期：2008.3

  Palladium-catalysed silylation of aryl iodides with electron-withdrawing groups was efficiently achieved using pyridine and lithium chloride as additives and conducting the reaction at room temperature. Functionalized aryl[2-(hydroxymethyl)phenyl]dimethylsilanes were also prepared by palladium-catalysed reaction using THP-protected [2-(hydroxymethyl)phenyl]dimethylsilane as a silylating agent followed

  使用吡啶和氯化锂作为添加剂并在室温下进行反应，可以有效地实现钯催化的带有吸电子基团的芳基碘化物的硅烷化。官能化的芳基[2-(羟甲基)苯基]二甲基硅烷也通过钯催化反应制备，使用THP保护的[2-(羟甲基)苯基]二甲基硅烷作为甲硅烷基化剂，然后去保护。使用环己烯酮作为烯酮以优异的产率进行芳基硅烷的铑催化1,4-加成。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Platinum Oxide Catalyzed Silylation of Aryl Halides with Triethylsilane:  An Efficient Synthetic Route to Functionalized Aryltriethylsilanes
  作者：Abdallah Hamze、Olivier Provot、Mouâd Alami、Jean-Daniel Brion

  DOI：10.1021/ol052996u

  日期：2006.3.2

  The first platinum-catalyzed selective silylation of aryl halides including aryl iodides and bromides having an electron-withdrawing group is described. The reaction takes place rapidly in NMP with triethylsilane as a silicon source and sodium acetate to provide functionalized aryltriethylsilanes in moderate to good yields. Heteroaromatic halides also were found to be readily silylated with triethylsilane. The procedure is chemoselective and tolerates a wide variety of functional groups.
• Direct and Selective Arylation of Tertiary Silanes with Rhodium Catalyst
  作者：Yoshinori Yamanoi、Hiroshi Nishihara

  DOI：10.1021/jo8008148

  日期：2008.9.1

  We have developed a convenient and efficient approach to the arylation of tertiary silanes under mild conditions. A variety of arylsilanes were synthesized in a one-step process with good to excellent yields in the presence of a rhodium catalyst with a base. The reaction was highly solvent dependent, and amides were the most effective of the various solvents used. This common catalyst system is highly tolerant of the various sensitive functional groups on the substrates, which might be difficult to extract by other methods. The rhodium-promoted silylation of aryl halides with electron-donating groups occurred more efficiently than the silylation of aryl halides substituted with electron-withdrawing groups. Heteroaromatic halides were also found to be readily silylated with tertiary silanes. The successful application of this reaction to the synthesis of a TAC-101 analogue, which is a trialkylsilyl-containing synthetic retinoid benzoic acid derivative with selective binding affinity for retinoic acid receptor-alpha, is also described.