2-biphenyl triisopropylsilylethynyl ether

• 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-biphenyl triisopropylsilylethynyl ether
• 英文别名: 2-(2-Phenylphenoxy)ethynyl-tri(propan-2-yl)silane；2-(2-phenylphenoxy)ethynyl-tri(propan-2-yl)silane
• 化学式: C₂₃H₃₀OSi
• 分子量: 350.576
• InChiKey: JLQAKBQMUAOEIT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.91
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 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：

  三乙基矽乙炔 、 2-biphenyl triisopropylsilylethynyl ether 在 1,1'-双(二苯基膦)二茂铁 、 copper(l) iodide 、 palladium diacetate 、 锌 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以96%的产率得到
  参考文献：
  名称：

  通过Pd /酸催化的CH键键活化2-芳氧基丁-1-烯3-炔烃的芳基化反应：2,3-双亚甲基-2,3-二氢苯并呋喃的简明合成

  摘要：

  分子内外的2-芳氧基- 1,4- disilylbut -1-烯-3-炔经由-hydroarylation邻-C-H键活化在钯（0）和酸催化被发现，得到2,3-双（silylmethylidene ）-2,3-二氢苯并呋喃。存在的两个甲硅烷基可能促进了反应并在稳定产物中的二烯部分中起关键作用。产物容易通过Diels-Alder反应导致官能化的冷凝循环。

  DOI：

  10.1002/asia.201701079
• 作为产物：
  描述：

  三异丙基氯硅烷 、 在 正丁基锂 、 六甲基磷酰三胺 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 15.17h， 生成 2-biphenyl triisopropylsilylethynyl ether
  参考文献：
  名称：

  Palladium-catalyzed Annulation of 2-Substituted Silylethynyloxybiaryls through δ-C–H Activation

  摘要：

  2-(硅烷基乙炔氧基)联苯在钯催化剂的作用下发生分子内氢芳基化反应，生成6-亚甲基-6H-二苯并[b,d]吡喃。产物可通过亲核脱硅反应转化为6,6-二取代二苯并吡喃，随后进行1,2-加成反应。1,4-双[2-(三异丙基硅烷基乙炔氧基)苯基]苯显示出双重分子内插入反应，导致形成五环缩合芳香族化合物。

  DOI：

  10.1246/cl.140725

文献信息

• Alkynoxy-Directed C–H Functionalizations: Palladium(0)-Catalyzed Annulations of Alkynyl Aryl Ethers with Alkynes
  作者：Yasunori Minami、Yuki Shiraishi、Tatsuro Kodama、Mayuko Kanda、Kotomi Yamada、Tomohiro Anami、Tamejiro Hiyama

  DOI：10.1246/bcsj.20150180

  日期：2015.10.15

  Palladium(0)-catalyzed insertion/annulation sequence between aryl silylethynyl ethers and internal alkynes was found to proceed through activation of ortho-C–H bonds assisted by alkynoxy groups and gave stereoselectively (Z)-2-silylmethylenechromenes. These products could be easily converted into 2,2-alkylated 2H-chromene derivatives, an important structural motif in medicinal chemistry and materials science. Various aryl silylethynyl ethers and alkynes can be transformed under the reaction conditions, and a wide range of chromenes is thus accessible. When unsymmetric alkynes are employed, a regioselective annulation takes place, especially those containing aryl and/or bulky substituents. Catalytic systems based on palladium(0), such as Pd(OAc)2/PCy3/Zn, [Pd(dba)2]/PCy3, or Pd(PCy3)2 exhibit excellent catalytic activity, and the best performance is observed for Pd(PCy3)2 in combination with Zn(OAc)2 as an additive. Substituents on the aryl group in the alkynyl aryl ethers rarely affect the reaction rate. Deuterium-labeling experiments suggest that the ortho-hydrogen atom migrates to the 2-methylene position in the chromene products. The cleavage of the C–H bond is considered to be the rate-determining step in these reactions.

  钯(0)催化的芳基硅乙炔醚与内烯的插入/环化反应发现，反应是通过烷炔醇基团辅助的邻位C–H键活化进行的，能够立体选择性地生成(Z)-2-硅基亚甲基色烯。这些产物可方便地转化为2,2-烷基化的2H-色烯衍生物，这在医药化学和材料科学中是一种重要的结构单元。在反应条件下，各种芳基硅乙炔醚和炔烃都可以被转化，因此可以获得广泛的色烯。当使用不对称炔烃时，会发生区域选择性的环化，特别是含有芳基和/或大取代基的情况。基于钯(0)的催化系统，如Pd(OAc)₂/PCy₃/Zn、[Pd(dba)₂]/PCy₃或Pd(PCy₃)₂展现出卓越的催化活性，并且在Pd(PCy₃)₂与Zn(OAc)₂作为添加剂结合时，表现最佳。阿尔基芳醚中芳基的取代基对反应速率几乎没有影响。氘标记实验表明，邻位氢原子迁移到色烯产物中的2-亚甲基位置。C–H键的断裂被认为是这些反应的速率决定步骤。
• Palladium-catalyzed annulation of alkynyl aryl ethers with isocyanates through o-C–H cleavage. Synthesis of solid-state emissive 2-methylidene-2H-1,4-benzoxazin-3(4H)-ones
  作者：Yasunori Minami、Mayuko Kanda、Megumi Sakai、Tamejiro Hiyama

  DOI：10.1016/j.tet.2015.02.062

  日期：2015.7

  The title transformation can be achieved by the o-C-H cleavage of allcynyl aryl ethers, which is easily derived from phenols, followed by the insertion/annulation with isocyanates in the presence of a palladium catalyst. Various alkynyl aryl ethers and arylisocyanates are applied to this transformation to give the corresponding cyclic products. Mechanistic study indicates that the C-H cleavage is effected reversibly by the concerted metalation-deprotonation pathway. The products exhibit solid-state luminescence upon irradiation of UV light. Fluorescent maxima and quantum yields can be controlled by the substituents at appropriate sites in the products. (C) 2015 Elsevier Ltd. All rights reserved.
• Palladium-catalyzed Annulation of 2-Substituted Silylethynyloxybiaryls through δ-C–H Activation
  作者：Yasunori Minami、Tomohiro Anami、Tamejiro Hiyama

  DOI：10.1246/cl.140725

  日期：2014.11.5

  The intramolecular hydroarylation of 2-(silylethynyloxy)biphenyls takes place with the aid of a palladium catalyst to give 6-methylene-6H-dibenzo[b,d]pyrans. The product can be transformed into 6,6-disubstituted dibenzopyrans via protodesilylation, followed by 1,2-addition. 1,4-Bis[2-(triisopropylsilylethynyloxy)phenyl]benzene is shown to undergo a dual intramolecular insertion reaction leading to the formation of pentacyclic condensed aromatics.

  2-(硅烷基乙炔氧基)联苯在钯催化剂的作用下发生分子内氢芳基化反应，生成6-亚甲基-6H-二苯并[b,d]吡喃。产物可通过亲核脱硅反应转化为6,6-二取代二苯并吡喃，随后进行1,2-加成反应。1,4-双[2-(三异丙基硅烷基乙炔氧基)苯基]苯显示出双重分子内插入反应，导致形成五环缩合芳香族化合物。
• Hydroarylation of 2‐Aryloxybut‐1‐en‐3‐ynes via Pd/Acid‐Catalyzed C−H Bond Activation: A Concise Synthesis of 2,3‐Bismethylene‐2,3‐dihydrobenzofurans
  作者：Yasunori Minami、Megumi Sakai、Takumi Sakamaki、Tamejiro Hiyama

  DOI：10.1002/asia.201701079

  日期：2017.9.19

  An intramolecular exo‐hydroarylation of 2‐aryloxy‐1,4‐disilylbut‐1‐en‐3‐ynes via ortho‐C−H bond activation under palladium(0) and acid catalysis was found to give 2,3‐bis(silylmethylidene)‐2,3‐dihydrobenzofurans. The two silyl groups present probably promoted the reaction and played a key role in stabilizing the diene moiety in the product. The products readily led to functionalized condensed cycles

  分子内外的2-芳氧基- 1,4- disilylbut -1-烯-3-炔经由-hydroarylation邻-C-H键活化在钯（0）和酸催化被发现，得到2,3-双（silylmethylidene ）-2,3-二氢苯并呋喃。存在的两个甲硅烷基可能促进了反应并在稳定产物中的二烯部分中起关键作用。产物容易通过Diels-Alder反应导致官能化的冷凝循环。