triethyl-[(Z)-2-[4-(trifluoromethyl)phenyl]ethenyl]silane | 1398694-66-0

• 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: triethyl-[(Z)-2-[4-(trifluoromethyl)phenyl]ethenyl]silane
• CAS: 1398694-66-0
• 化学式: C₁₅H₂₁F₃Si
• 分子量: 286.412
• InChiKey: ARWVYKKLZKQEKI-QXMHVHEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.77
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  三乙基硅烷 、 4-乙炔基-α,α,α-三氟甲苯 在 Cp*RhCl{(MeIm)₂CHCOO} 作用下， 以 氘代氯仿 为溶剂， 反应 24.0h， 生成 triethyl-[(Z)-2-[4-(trifluoromethyl)phenyl]ethenyl]silane
  参考文献：
  名称：

  两性离子双-NHC铑（III）配合物催化末端炔烃的羧酸盐辅助β-（Z）立体选择性氢化硅烷化

  摘要：

  两性离子化合物[Cp * RhCl {（MeIm）2 CHCOO}]是一种有效的催化剂，可在温和的反应条件下，使末端炔烃对热力学上较不稳定的β-（Z）-乙烯基硅烷异构体具有出色的区域选择性和立体选择性。各种各样的线性1-炔烃，环烷基乙炔和芳族炔烃与HSiMe 2 Ph进行氢化硅烷化反应，可以在较短的反应时间内以定量收率得到相应的β-（Z）-乙烯基硅烷。脂族炔烃与HSiEt 3的反应较慢，导致对β-（Z的选择性略微降低）-乙烯基硅烷产物，其仍大于90％。然而，由于β-（Z）→β-（E）乙烯基硅烷异构化，在芳族炔烃的氢化硅烷化中观察到显着的选择性降低。此外，大体积炔烃（如t -Bu–C≡CH或Et 3）的氢化硅烷化SiC≡CH是非选择性的。实验证据表明，羧酸盐功能在反应机理中起着关键作用，已通过密度泛函理论计算以及质谱和标记研究进行了验证。根据先前的结果，我们提出了一种离子外球机理途径，其中羧

  DOI：

  10.1021/acscatal.0c01582

文献信息

• Experimental and Computational Studies of the Ruthenium-Catalyzed Hydrosilylation of Alkynes: Mechanistic Insights into the Regio- and Stereoselective Formation of Vinylsilanes
  作者：Ruili Gao、Dale R. Pahls、Thomas R. Cundari、Chae S. Yi

  DOI：10.1021/om501019j

  日期：2014.12.8

  regio- and stereoselective hydrosilylation of alkynes to form vinylsilane products. (Z)-Vinylsilane products were selectively formed for sterically nondemanding terminal alkynes, while (E)-vinylsilane products resulted from sterically demanding terminal alkynes. Kinetic data were obtained from the hydrosilylation of phenylacetylene. The phosphine inhibition study showed an uncompetitive Michaelis–Menten

  氢化钌络合物（PCy 3）2（CO）RuHCl被发现是炔烃区域和立体选择性氢化硅烷化形成乙烯基硅烷产物的高效催化剂。（Z）-乙烯基硅烷产物是选择性形成的，用于空间上不要求的末端炔烃，而（E）-乙烯基硅烷产物是由空间上需要的末端炔烃产生的。动力学数据是从苯乙炔的氢化硅烷化获得的。磷化氢的抑制作用研究表明，Michaelis-Menten的抑制动力学没有竞争性。经验率定律率= k obs [ 1 ] 1 [炔烃] 0 [硅烷] 0根据[炔烃]和[硅烷]两者的函数，确定反应速率。进行了DFT计算，发现通过金属-环丙烯过渡态Z / E异构化很容易，并且异构化发生在与硅烷底物结合之前。在实验和计算数据的基础上，描述了有关氢化硅烷化反应的详细机理。
• 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。
• An Alternative Mechanistic Paradigm for the β‐ <i>Z</i> Hydrosilylation of Terminal Alkynes: The Role of Acetone as a Silane Shuttle
  作者：Manuel Iglesias、Pablo J. Sanz Miguel、Victor Polo、Francisco J. Fernández‐Alvarez、Jesús J. Pérez‐Torrente、Luis A. Oro

  DOI：10.1002/chem.201303063

  日期：2013.12.16

  model. Heterolytic splitting of the silane molecule by the metal centre and acetone (solvent) affords a metal hydride and the oxocarbenium ion [R3SiO(CH3)2]+, which reacts with the corresponding alkyne in solution to give the silylation product [R3SiCHCR]+. Thus, acetone acts as a silane shuttle by transferring the silyl moiety from the silane to the alkyne. Finally, nucleophilic attack of the

  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
• 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.