cis-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: cis-3,3-dimethyl-1-(diphenylmethylsilyl)-1-butene
• 英文别名: [(Z)-3,3-dimethylbut-1-enyl]-methyl-diphenylsilane
• 化学式: C₁₉H₂₄Si
• 分子量: 280.485
• InChiKey: ZBPQVFPXOFDLNV-NXVVXOECSA-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：

  3,3-二甲基-1-丁炔 、 二苯甲基硅烷 在 [IrH(κ³-8-oxidoquinoline-2-carboxylate)(cyclooctene)] 作用下， 以 氘代氯仿 为溶剂， 反应 1.0h， 生成 3,3-二甲基-1-丁烯 、 cis-3,3-dimethyl-1-(diphenylmethylsilyl)-1-butene 、 trans-3,3-dimethyl-1-(diphenylmethylsilyl)-1-butene
  参考文献：
  名称：

  ONO-Pinc铱（III）氢化物催化的末端炔烃的氢化硅烷化：对氢化硅烷化和脱氢硅烷化催化的机理研究

  摘要：

  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.

  DOI：

  10.1021/acs.organomet.6b00471

文献信息

• 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.