trans-3,3-dimethyl-1-(diphenylmethylsilyl)-1-butene

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: trans-3,3-dimethyl-1-(diphenylmethylsilyl)-1-butene
• 英文别名: [(E)-3,3-dimethylbut-1-enyl]-methyl-diphenylsilane
• 化学式: C₁₉H₂₄Si
• 分子量: 280.485
• InChiKey: ZBPQVFPXOFDLNV-FOCLMDBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.02
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 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：

  甲基二苯基氯硅烷 在 lithium 、 copper(II) iodide 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 trans-3,3-dimethyl-1-(diphenylmethylsilyl)-1-butene
  参考文献：
  名称：

  乙炔的甲硅烷基化

  摘要：

  已经制备了几种有机甲硅烷基铜酸酯，并检查了它们与乙炔的反应。已经表明，LiCu [Si（SiMe 3）3 ] 2仅以一种方式加到乙炔中，即顺式加成，Si（SiMe 3）3基团受阻最小，如下式所示。类似地，位阻LiCu（SiMePh 2）2 LiCu [Si（SiMe 3）2 ] 2 ·LiI +RCCH→H +，H 2 O→反式-RHCCHSi（SiMe 3）3仅以这种方式添加。如果使用位阻较小的锂化合物LiSiMe 2 Ph来制备铜试剂，则当Li / Cu比例降低为产物和混合物A和B时（SiR 3 = SiMe 2 Ph; R'= N =丁基）中的比率而获得，但只有一个产物，甲（SIR 3 =森达2 Ph值; R'=正丁基，叔卜中，Ph），当锂/ Cu的比率获得。仅甲获得当任diphenylmethylsilyllithium或三（三甲硅烷基）silyllithium（SIR 3 =

  DOI：

  10.1016/0022-328x(86)80494-6

文献信息

• Efficient Pd(0)-Catalyzed Hydrosilylation of Alkynes with Triorganosilanes
  作者：Koichiro Oshima、Dai Motoda、Hiroshi Shinokubo

  DOI：10.1055/s-2002-33535

  日期：——

  An electron-rich Pd(0) complex, a Pd 2 (dba) 3 .CHCl 3 -tri-cyclohexylphosphine combination catalyzes highly efficient hydrosilylation of alkynes at room temperature with Ph 3 SiH or Ph 2 MeSiH without solvents. The regioselectivity of this process is higher than that with the conventional Pt(0)-catalyzed hydrosilylation.

  一种富含电子的 Pd(0) 络合物，即 Pd 2 (dba) 3 .CHCl 3 -三环己基膦组合，在室温下用 Ph 3 SiH 或 Ph 2 MeSiH 在没有溶剂的情况下催化炔烃的高效氢化硅烷化。该过程的区域选择性高于传统的 Pt(0) 催化氢化硅烷化。
• 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.
• CHEN HSIAO-MING; OLIVER J. P., J. ORGANOMET. CHEM., 316,(1986) N 3, 255-260
  作者：CHEN HSIAO-MING、 OLIVER J. P.

  DOI：——

  日期：——
• Silylcupration of acetylenes
  作者：Hsiao-Ming Chen、John P. Oliver

  DOI：10.1016/0022-328x(86)80494-6

  日期：1986.12

  their reactions with acetylenes examined. It has been shown that LiCu[Si(SiMe3)3]2 adds to acetylenes in only one manner, i.e. with cis addition and the Si(SiMe3)3 group in the least hindered cite as shown in the equation below. Similarly the sterically hindered LiCu(SiMePh2)2 LiCu[Si(SiMe3)2]2·LiI + RCCH → H+,H2O → trans-RHCCHSi(SiMe3)3 adds only in this fashion. If the less sterically hindered lithium

  已经制备了几种有机甲硅烷基铜酸酯，并检查了它们与乙炔的反应。已经表明，LiCu [Si（SiMe 3）3 ] 2仅以一种方式加到乙炔中，即顺式加成，Si（SiMe 3）3基团受阻最小，如下式所示。类似地，位阻LiCu（SiMePh 2）2 LiCu [Si（SiMe 3）2 ] 2 ·LiI +RCCH→H +，H 2 O→反式-RHCCHSi（SiMe 3）3仅以这种方式添加。如果使用位阻较小的锂化合物LiSiMe 2 Ph来制备铜试剂，则当Li / Cu比例降低为产物和混合物A和B时（SiR 3 = SiMe 2 Ph; R'= N =丁基）中的比率而获得，但只有一个产物，甲（SIR 3 =森达2 Ph值; R'=正丁基，叔卜中，Ph），当锂/ Cu的比率获得。仅甲获得当任diphenylmethylsilyllithium或三（三甲硅烷基）silyllithium（SIR 3 =