2-dimethylphenylsilylbiphenyl | 1316335-57-5

• 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: 2-dimethylphenylsilylbiphenyl
• 英文别名: [1,1'-biphenyl]-2-yldimethyl(phenyl)silane；Dimethyl-phenyl-(2-phenylphenyl)silane；dimethyl-phenyl-(2-phenylphenyl)silane
• CAS: 1316335-57-5
• 化学式: C₂₀H₂₀Si
• 分子量: 288.464
• InChiKey: IKNOCCJHXSJPGH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.18
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  dimethyl(phenyl)silyl lithium 在 二氯化双(三环己基膦)镍(II) 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 2-dimethylphenylsilylbiphenyl
  参考文献：
  名称：

  芳基2-吡啶基醚与氯化硅锌的镍催化反应：通过碳氧键的裂解使芳基2-吡啶基醚甲硅烷基化

  摘要：

  进行了Ni催化的C-O（Py）键活化和芳基2-吡啶基醚与甲硅烷基氯化锌的甲硅烷基化反应。该方案允许2-吡啶氧基被甲硅烷基取代，反应时间短，反应条件温和且官能团相容性好。

  DOI：

  10.1002/adsc.201900949

文献信息

• <i>In Situ</i>Generation of Silyl Anion Species through Si−B Bond Activation for the Concerted Nucleophilic Aromatic Substitution of Fluoroarenes
  作者：Kumiko Kojima、Yuki Nagashima、Chao Wang、Masanobu Uchiyama

  DOI：10.1002/cplu.201900069

  日期：2019.3

  pathway with an activation barrier of ca. 20 kcal/mol to afford the silylated product with a large energy gain. Experiments confirmed that the defluorosilylation reaction took place smoothly at room temperature simply upon mixing fluoroarenes with commercially available silylborane and NaOt Bu. Radical scavenger and radical clock reaction experiments provide further evidence for the in situ generation

  原位生成的甲硅烷基阴离子可实现氟代芳烃的协同亲核芳香取代。DFT模型的计算表明，向甲硅烷基硼烷中添加碱会热力学上形成甲硅烷基硼酸酯络合物，然后通过Si-B键断裂而动态释放甲硅烷基阴离子，并且原位生成的甲硅烷基阴离子当量还会与氟代芳烃通过激活亲核取代的协调亲核芳香族途径。20 kcal / mol可提供具有较大能量增益的甲硅烷基化产物。实验证实，仅在将氟代芳烃与市售甲硅烷基硼烷和NaOt Bu混合后，脱氟硅烷化反应即可在室温下顺利进行。
• Efficient Access to Substituted Silafluorenes by Nickel-Catalyzed Reactions of Biphenylenes with Et₂SiH₂
  作者：Jens Michael Breunig、Puneet Gupta、Animesh Das、Samat Tussupbayev、Martin Diefenbach、Michael Bolte、Matthias Wagner、Max C. Holthausen、Hans-Wolfram Lerner

  DOI：10.1002/asia.201402599

  日期：2014.11

  [Ni(PPhMe2)4]‐catalyzed reaction of Et2SiH2 and 1‐methylbiphenylene. By contrast, no selectivity could be found in the Ni‐catalyzed reaction between Et2SiH2 and the biphenylene derivative that bears tBu substituents in the 2‐ and 7‐positions. Therefore, two pairs of isomers of tBu‐substituted silafluorenes and of the related diethylhydrosilylbiphenyls were formed in this reaction. However, a subsequent

  在[Ni（PPhMe 2）4 ]存在下，联苯（1）与Et 2 SiH 2的反应导致形成2-二乙基氢甲硅烷基联苯[ 2（Et 2 HSi）]和9,9，-二乙基的混合物‐9‐硅芴（3）。分离出37.5％的Silafluorene 3和36.9％的产率的2（Et 2 HSi）。通过DFT计算阐明了潜在的反应机理。由[Ni（PPhMe 2）4 ]催化的Et 2 SiH反应选择性地获得了4-甲基-9,9-二乙基-9-硅芴（7）2和1-甲基联苯。相比之下，在Et 2 SiH 2和在2位和7位带有t Bu取代基的联苯衍生物之间的Ni催化反应中，没有发现选择性。因此，在该反应中形成了t Bu-取代的硅芴和相关的二乙基氢甲硅烷基联苯的两对异构体。但是，随后用威尔金森氏催化剂将二乙基氢甲硅烷基联苯脱氢，得到了2,7-二叔丁基-9,9-二乙基-9-硅芴（8）和3,6-二叔丁基9的混合物， 9-二乙基-9-硅芴（9）。硅芴8和9
• Palladium-Catalyzed Hydrometalation and Bismetalation of Biphenylene
  作者：Takanori Matsuda、Haruki Kirikae

  DOI：10.1021/om200436d

  日期：2011.8.8

  2-Silyl- and 2-borylbiphenyls have been synthesized by the palladium-catalyzed reaction of biphenylene with hydrosilanes and a hydroborane, respectively, via the cleavage of the four-membered ring of biphenylene. Under similar conditions, the C-C bond of biphenylene undergoes formal sigma-bond metathesis with various intermetallic linkages to afford 2,2'-bis(metallo)biphenyls.
• Nickel‐Catalyzed Reaction of Aryl 2‐Pyridyl Ethers with Silylzinc Chlorides: Silylation of Aryl 2‐Pyridyl Ethers via Cleavage of the Carbon−Oxygen Bond
  作者：Ying‐Ying Kong、Zhong‐Xia Wang

  DOI：10.1002/adsc.201900949

  日期：2019.12.3

  Ni‐catalyzed C−O(Py) bond activation and silylation of aryl 2‐pyridyl ethers with silylzinc chlorides were carried out. This protocol allowed the 2‐pyridyloxy group to be substituted by a silyl group with short reaction times, mild reaction conditions, and good compatibility of functional groups.

  进行了Ni催化的C-O（Py）键活化和芳基2-吡啶基醚与甲硅烷基氯化锌的甲硅烷基化反应。该方案允许2-吡啶氧基被甲硅烷基取代，反应时间短，反应条件温和且官能团相容性好。