(Z)-(4-methoxystyryl)(methyl)diphenylsilane | 1398694-60-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (Z)-(4-methoxystyryl)(methyl)diphenylsilane
• 英文别名: [(Z)-2-(4-methoxyphenyl)ethenyl]-methyl-diphenylsilane
• CAS: 1398694-60-4
• 化学式: C₂₂H₂₂OSi
• 分子量: 330.502
• InChiKey: AVXQRGIRHHWTFR-ZCXUNETKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.14
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  二苯甲基硅烷 、 4-乙炔基苯甲醚 在 methylenebis((N-2-methoxyethyl-κO,κO’)imidazole-2-ylidene)-(diiodo)rhodium(III) tetrafluoroborate 作用下， 以 氘代丙酮 为溶剂， 反应 5.0h， 生成 (Z)-(4-methoxystyryl)(methyl)diphenylsilane
  参考文献：
  名称：

  末端炔烃β-Z氢化硅烷化的另一种机制范式：丙酮作为硅烷穿梭的作用

  摘要：

  迄今为止，通过在经典机理中引入异构化步骤，可以解释末端炔烃的氢化硅烷化中的β- Z选择性。系统[M（I）2 {κ-C，C，O，O-（bis-NHC）}] BF 4（M = Ir（3 a），Rh（3 b）; bis的DFT计算和实验观察‐NHC =亚甲基双（N -2-甲氧基乙基）咪唑-2-亚基）支持一种新机制，可替代基于外层模型的经典假设。由金属中心和丙酮（溶剂）硅烷分子的异裂分裂，得到一个金属氢化物和oxocarbenium离子[R 3的Si  O（CH 3）2 ]+，其中发生反应与溶液中的相应的炔，得到甲硅烷基化产物[R 3的Si  CHC  R] +。因此，丙酮通过将甲硅烷基部分从硅烷转移至炔烃而充当硅烷穿梭。最后，将氢基的亲核进攻配体在[R 3的Si  CHC  R] +，得到选择性地将β-（Ž）-vinylsilane。β- Z选择性的解释是基于产生β-（E）-乙烯基

  DOI：

  10.1002/chem.201303063

文献信息

• Dichotomy of Manganese Catalysis via Organometallic or Radical Mechanism: Stereodivergent Hydrosilylation of Alkynes
  作者：Xiaoxu Yang、Congyang Wang

  DOI：10.1002/anie.201710206

  日期：2018.1.22

  Herein, we disclose the first manganese‐catalyzed hydrosilylation of alkynes featuring diverse selectivities. The highly selective formation of E‐products was achieved by using mononuclear MnBr(CO)5 with the arsenic ligand, AsPh3. Whereas using the dinuclear catalyst Mn2(CO)10 and LPO (dilauroyl peroxide) enabled the reversed generation of Z‐products in good to excellent stereo‐ and regioselectivity

  本文中，我们公开了具有多种选择性的炔烃的首次锰催化氢化硅烷化反应。通过使用具有砷配体AsPh 3的单核MnBr（CO）5可以实现E产品的高度选择性形成。而使用双核催化剂Mn 2（CO）10和LPO（过氧化二月桂酰二氧戊二烯）可以实现Z产物的反向生成，具有良好的立体选择性和区域选择性。这种控制反应立体选择性的方法是前所未有的。机理实验揭示了通过E-和Z上运行的有机金属和自由基途径对锰催化作用的二分法选择性路线。
• A synthon for a 14-electron Ir(iii) species: catalyst for highly selective β-(Z) hydrosilylation of terminal alkynes
  作者：Manuel Iglesias、María Pérez-Nicolás、Pablo J. Sanz Miguel、Victor Polo、Francisco J. Fernández-Alvarez、Jesús J. Pérez-Torrente、Luis A. Oro

  DOI：10.1039/c2cc34931k

  日期：——

  A synthon for a 14-electron Ir(III) species is described. The geometrical control exerted by the ligand system over the Ir–alkenyl intermediate in hydrosilylation of terminal alkynes precludes formation of the more thermodynamically stable β-(E)-vinylsilane, thus affording the β-(Z) isomer in excellent yields.

  本文描述了一种 14 电子铱（III）的合成物。在末端炔烃的氢硅化过程中，配体系统对烷基铱中间体的几何控制排除了形成热力学上更稳定的δ-(E)-乙烯基硅烷的可能性，从而以优异的收率获得了δ-(Z)异构体。
• β-(<i>Z</i>)-Selective alkyne hydrosilylation by a N,O-functionalized NHC-based rhodium(<scp>i</scp>) catalyst
  作者：Miguel González-Lainez、M. Victoria Jiménez、Vincenzo Passarelli、Jesús J. Pérez-Torrente

  DOI：10.1039/d3dt01911j

  日期：——

  Neutral and cationic cyclooctadiene rhodium(I) complexes with a lutidine-derived polydentate ligand having NHC and methoxy side-donor functions, [RhBr(cod)(κC-tBuImCH2PyCH2OMe)] and [Rh(cod)(κ2C,N-tBuImCH2PyCH2OMe)]PF6, have been prepared. Carbonylation of the cationic compound yields the dicarbonyl complex [Rh(CO)2(κ2C,N-tBuImCH2PyCH2OMe)]PF6 whereas carbonylation of the neutral compound affords a

  中性和阳离子环辛二烯铑 ( I ) 与具有 NHC 和甲氧基侧供体功能的二甲基吡啶衍生的多齿配体的络合物，[RhBr(cod)(κC- t BuImCH 2 PyCH 2 OMe)] 和 [Rh(cod)(κ 2 )已制备出C,N- t BuImCH 2 PyCH 2 OMe)]PF 6 。阳离子化合物的羰基化产生二羰基络合物 [Rh(CO) 2 (κ 2 C,N- t BuImCH 2 PyCH 2 OMe)]PF 6而中性化合物的羰基化产生二羰基和单羰基中性络合物的混合物 [RhBr (CO) 2 (κC- t BuImCH 2 PyCH 2 OMe)]和[RhBr(CO)(κ 2 C,N- t BuImCH 2 PyCH 2 OMe)]。这些配合物有效催化 1-己炔与 HSiMe 2 Ph 的氢化硅烷化反应，对 β-( Z )-乙烯基硅烷产物具有显着的选择性。催化剂[RhBr(CO)(κ
• Hydrosilylation of Terminal Alkynes Catalyzed by a ONO-Pincer Iridium(III) Hydride Compound: Mechanistic Insights into the Hydrosilylation and Dehydrogenative Silylation Catalysis
  作者：Jesús J. Pérez-Torrente、Duc Hanh Nguyen、M. Victoria Jiménez、F. Javier Modrego、Raquel Puerta-Oteo、Daniel Gómez-Bautista、Manuel Iglesias、Luis A. Oro

  DOI：10.1021/acs.organomet.6b00471

  日期：2016.7.25

  The catalytic activity in the hydrosilylation of terminal alkynes by the unsaturated hydrido iridium(III) compound [IrH(kappa(3)-hqca)(coe)] (1), which contains the rigid asymmetrical dianionic ONO pincer ligand 8-oxidoquinoline-2-carboxylate, has been studied. A range of aliphatic and aromatic 1-alkynes has been efficiently reduced using various hydrosilanes. Hydrosilylation of the linear 1-alkynes hex-1-yne and oct-1-yne gives a good selectivity toward the beta-(Z)-vinylsilane product, while for the bulkier t-Bu-C CH a reverse selectivity toward the beta-(E)-vinylsilane and significant amounts of alkene, from a competitive dehydrogenative silylation, has been observed. Compound 1, unreactive toward silanes, reacts with a range of terminal alkynes RC CH, affording the unsaturated eta(1)-alkenyl complexes [Ir(kappa(3)-hqca)(E-CH=CHR)(coe)] in good yield. These species are able to coordinate monodentate neutral ligands such as PPh3 and pyridine, or CO in a reversible way, to yield octahedral derivatives. Further mechanistic aspects of the hydrosilylation process have been studied by DFT calculations. The catalytic cycle passes through Ir(III) species with an iridacyclopropene (eta(2)-vinylsilane) complex as the key intermediate. It has been found that this species may lead both to the dehydrogenative silylation products, via a beta-elimination process, and to a hydrosilylation cycle. The beta-elimination path has a higher activation energy than hydrosilylation. On the other hand, the selectivity to the vinylsilane hydrosilylation products can be accounted for by the different activation energies involved in the attack of a silane molecule at two different faces of the iridacyclopropene ring to give eta(1)-vinylsilane complexes with either an E or Z configuration. Finally, proton transfer from a eta(2)-silane to a eta(1)-vinylsilane ligand results in the formation of the corresponding beta-(Z)- and beta-(E)-vinylsilane isomers, respectively.