二甲基(己-1-烯基)(苯基)硅烷 | 299964-01-5

• 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
• 中文名称: 二甲基(己-1-烯基)(苯基)硅烷
• 英文名称: dimethyl(hex-1-enyl)(phenyl)silane
• 英文别名: 1-(dimethylphenylsilyl)hexene；Hex-1-enyl-dimethyl-phenylsilane
• CAS: 299964-01-5
• 化学式: C₁₄H₂₂Si
• 分子量: 218.414
• InChiKey: PTVTWWVOURXNJF-UHFFFAOYSA-N

物化性质

• 沸点：
  271.4±9.0 °C(Predicted)
• 密度：
  0.87±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.89
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  二甲基(己-1-烯基)(苯基)硅烷 在 正丁基锂 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 5.0h， 生成 3-Butylcyclohepta-1,5-diene-1-carbonitrile
  参考文献：
  名称：

  Synthesis of 2-cyano-1,4-cycloheptadiene derivatives via divinylcyclopropane rearrangement and alkylation of novel cycloheptadienyl anion species

  摘要：

  An efficient synthetic method for 2-cyano-1,4-cycloheptadiene derivatives was developed on the basis of divinylcyclopropane rearrangement. The substrates were prepared from 2-vinylcyclopropanecarbonitrile and an alpha,beta-epoxysilane through a Peterson olefination. The resulting 2-cyano-1,4-cycloheptadiene underwent deprotonation at the doubly allylic methylene group to afford a novel cycloheptadienyl anion, a useful intermediate for synthesizing polycyclic compounds. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.11.070
• 作为产物：
  描述：

  苯基二甲基氯硅烷 在 偶氮二异丁腈 作用下， 以 正己烷 为溶剂， 生成 二甲基(己-1-烯基)(苯基)硅烷
  参考文献：
  名称：

  自由基链氢化硅烷化中的硅烷化环己二烯

  摘要：

  描述了烯烃和炔烃的温和自由基氢化硅烷化的新方法。可以容易地大规模制备的甲硅烷基化环己二烯被用作自由基氢化硅烷化试剂。非活化烯烃和炔烃以高产率氢化硅烷化。该反应可以与 CC 键的形成相结合，如从相应的二烯制备甲硅烷基化环烷烃所证明的那样。此外，自由基氢化硅烷化与β-断裂反应相结合用于合成烯丙基硅烷和醛和酮的氢化硅烷化提供受保护的醇可以很容易地通过该策略进行。

  DOI：

  10.1002/1522-2675(200210)85:10<3559::aid-hlca3559>3.0.co;2-6

文献信息

• Modular Synthesis of a Versatile Double‐Allylation Reagent for Complex Diol Synthesis
  作者：Stanna K. Dorn、Annika E. Tharp、M. Kevin Brown

  DOI：10.1002/anie.202103435

  日期：2021.7.12

  Double-allylation reagents allow for the construction of highly complex molecules in an expedient fashion. We have developed an efficient, modular, and enantioselective approach towards accessing novel variants of these reagents through Cu/Pd-catalyzed alkenylboration of alkenylboron derivatives. Importantly, we demonstrate novel use of an allylBdan reagent directly in a stereocontrolled allylation

  双烯丙基化试剂允许以便利的方式构建高度复杂的分子。我们开发了一种高效、模块化和对映选择性的方法，通过铜/钯催化烯基硼衍生物的烯基硼化反应来获得这些试剂的新变体。重要的是，我们证明了烯丙基Bdan试剂直接在立体控制烯丙基化中的新用途，而无需对硼酸酯进行初始脱保护。这些烯丙基化产物用于第二次分子间烯丙基化以获得复杂的二醇基序，这尚未用这些类型的双烯丙基化试剂来证明。总的来说，这种方法的模块化以及快速访问复杂结构主题的便利性表明了这种方法的重要性和实用性。
• Alkenyl-functionalized NHC iridium-based catalysts for hydrosilylation
  作者：Alessandro Zanardi、Eduardo Peris、Jose A. Mata

  DOI：10.1039/b707280e

  日期：——

  A family of alkenyl-functionalized N-heterocyclic-carbene–iridium(I) complexes has been synthesized, providing a series of mono-coordinated, bis-chelate and pinceralkenyl-NHC species. Olefin coordination is highly influenced by the nature of the substituents on the NHC ring, and on the length of the alkenyl branch. A fluxional process involving coordination/decoordination of the olefin in bis-allyl-NHC complexes has been studied, and the activation parameters have been determined by means of VT-NMR spectroscopy. The mono-coordinated complexes are highly active in the hydrosilylation of terminal alkynes, showing high selectivity for the Z-isomers, with no α-isomers or dehydrogenative silylation processes being observed. The molecular structures reported that are representative of the species have been determined by means of X-ray crystallography.

  我们合成了一系列烯基官能化的 N-杂环碳-铱（I）络合物，提供了一系列单配位、双螯合和钳烯基-NHC 种类。烯烃配位受 NHC 环上取代基的性质和烯烃支长度的影响很大。我们研究了双烯丙基-NHC 复合物中烯烃配位/脱配位的通量过程，并通过 VT-NMR 光谱测定了活化参数。单配位配合物在末端炔烃的氢化硅烷化过程中具有很高的活性，对 Z-异构体具有很高的选择性，没有观察到 α-异构体或脱氢硅烷化过程。报告中具有代表性的分子结构是通过 X 射线晶体学确定的。
• Silylformylation of Chiral 1-Alkynes, Catalysed by Solvated Rhodium Atoms
  作者：Laura Antonella Aronica、Silvia Terreni、Anna Maria Caporusso、Piero Salvadori

  DOI：10.1002/1099-0690(200111)2001:22<4321::aid-ejoc4321>3.0.co;2-t

  日期：2001.11

  Solvated rhodium atoms, prepared by the metal vapour synthesis technique, promote the silylformylaton reaction of variously substituted alkynes (RRCH)-R-1-C-2(CH2)(n)C equivalent to CH, with catalytic activities comparable with and even higher than more common species such as Rh-4(CO)(12). Z-Silylalkenals are exclusively formed in high yields (60-95%) indicating syn addition both of CO and of the silane (Me2PhSiH) to the triple bond, The chemoselectivity of the process (silylformylation vs. hydrosilylation) is highly affected by the amount of catalyst employed (mmol of Rh species with respect to the alkyne reagent), by the steric requirements of the acetylenic substrates and by the hydrosilane/alkyne molar ratio. When optically active acetylenes are treated in the presence of Me2PhSiH under carbon monoxide pressure, the silylformylation reaction occurs with total retention of stereochemistry of the stereogenic centre, even if it is at the alpha -position of the unsaturated moiety, to afford enantiomerically enriched beta -silylalkenals.
• Rhodium(II) complexes as hydrosilylation and hydrogenation catalysts
  作者：J.P. Howe、K. Lung、Terence A. Nile

  DOI：10.1016/s0022-328x(00)86724-8

  日期：1981.3
• Synthesis of 2-cyano-1,4-cycloheptadiene derivatives via divinylcyclopropane rearrangement and alkylation of novel cycloheptadienyl anion species
  作者：Takumasa Yamada、Fumihiko Yoshimura、Keiji Tanino

  DOI：10.1016/j.tetlet.2012.11.070

  日期：2013.2

  An efficient synthetic method for 2-cyano-1,4-cycloheptadiene derivatives was developed on the basis of divinylcyclopropane rearrangement. The substrates were prepared from 2-vinylcyclopropanecarbonitrile and an alpha,beta-epoxysilane through a Peterson olefination. The resulting 2-cyano-1,4-cycloheptadiene underwent deprotonation at the doubly allylic methylene group to afford a novel cycloheptadienyl anion, a useful intermediate for synthesizing polycyclic compounds. (C) 2012 Elsevier Ltd. All rights reserved.