1-(triphenylsilyl)-1-hexyne | 96475-96-6

• 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: 1-(triphenylsilyl)-1-hexyne
• 英文别名: Hex-1-ynyl(triphenyl)silane
• CAS: 96475-96-6
• 化学式: C₂₄H₂₄Si
• 分子量: 340.54
• InChiKey: ZPZWFBVVNHYCFL-UHFFFAOYSA-N

物化性质

• 沸点：
  423.3±18.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.89
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  1-(triphenylsilyl)-1-hexyne 在 碘 、 二异丁基氢化铝 作用下， 生成 (E)-1-Iodo-1-(triphenylsilyl)-1-hexene
  参考文献：
  名称：

  Charge-directed conjugate addition reactions of silylated .alpha.,.beta.-unsaturated amidate anions

  摘要：

  A variety of N-substituted alpha-silylated-alpha,beta-unsaturated amidate anions (2) have been found to be excellent Michael acceptors in charge-directed conjugate addition reactions with Grignard and organolithium reagents. The effects of olefin substitution, Si-substitution, N-substitution, and amidate counterion have been studied. Anionic acceptors may be prepared in situ by the addition of silylated vinyllithium reagents to isocyanates and then allowed to undergo conjugate addition reactions with subsequently added nucleophiles, but it was found to be more efficient to isolate neutral acceptors and regenerate the acceptor anion through the use of excess nucleophile. Beta-Substituted acceptors were found to react only with reactive organolithium reagents while a beta,beta-disubstituted acceptor failed to undergo conjugate addition reactions. A primary amide acceptor (14d) also undergoes addition reactions with larger quantitites of nucleophiles suggesting that dianionic amidate acceptors (31) are involved. Diene acceptor 24 was found to undergo a 1,6-addition reaction with n-BuLi. Sodium and potassium amidate salts were found to be inferior to lithium and magnesium salts in addition reactions in keeping with the expectation that an increase in carbonyl-group charge burden retards conjugate reactions. Triphenylsilyl-containing acceptor 16 was found to be more reactive in reactions with n-BuMgCl but less reactive with bulkier tert-BuMgCl. Adduct dianions can be monoalkylated with alkyl iodides and used in Peterson olefination reactions.

  DOI：

  10.1021/jo00078a028
• 作为产物：
  描述：

  三苯基氯硅烷 、 1-己炔 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以74%的产率得到1-(triphenylsilyl)-1-hexyne
  参考文献：
  名称：

  有机金属化合物的立体化学：XXXVI。镍催化的甲硅烷基炔烃氢氰化中的区域和立体化学控制

  摘要：

  可以通过改变与硅相连的基团的大小来控制甲硅烷基炔烃的氢氰化的区域选择性，所述硅导致例如高效制备E -3-三烷基甲硅烷基-2-烷基-2-烯腈。通过使用丙酮氰醇或氰化氢作为试剂，可以获得高产率的甲硅烷基烯烃腈。

  DOI：

  10.1016/0022-328x(85)87381-2

文献信息

• Synthesis of lanthanide(II)–imine complexes and their use in carbon–carbon and carbon–nitrogen unsaturated bond transformation
  作者：Ken Takaki、Kimihiro Komeyama、Katsuomi Takehira

  DOI：10.1016/j.tet.2003.06.003

  日期：2003.12

  1 quantitatively, the structure of which was characterized by X-ray analysis. The imine complexes 1 catalyzed dehydrogenative silylation of terminal alkynes, hydrosilylation of imines and alkenes, and intermolecular hydrophosphination of alkynes. Moreover, dehydrogenative double silylation of conjugated dienes was achieved with 1.

  和sa金属将芳香族酮亚胺还原，直接定量得到二价氮杂蒽环丙烷丙烷配合物1，其结构通过X射线分析表征。亚胺络合物1催化末端炔烃的脱氢甲硅烷基化，亚胺和烯烃的氢化硅烷化以及炔烃的分子间加氢磷酸化。此外，共轭二烯的脱氢双甲硅烷基化是用1实现的。
• Regio- and stereo-chemical control in the nickel-catalysed addition of HCN to alkynes. A simple synthesis of (E)-2-alkyl-3-trialkylsilylalk-2-enenitriles
  作者：Gary D. Fallon、Neil J. Fitzmaurice、W. Roy Jackson、Patrick Perlmutter

  DOI：10.1039/c39850000004

  日期：——

  it is p ossible to control, to a high degree, the regiochemical outcome of nickel(0)-catalysed hydrocyanations of alk-1-ynes: the crystal structure of one adduct is included which establishes that the stereochemical outcome of the reaction is a result of addition of HCN to the alkyne to give an (E)-product; overall, these results constitute a simple method for the preparation of (E)-2-alkyl-3-trialk

  通过改变与alk-1-ynes相连的硅取代基的空间体积，可以高度控制镍（0）催化的alk-1-ynes氢氰化的区域化学结果：一种晶体的结构包括加合物，其确定反应的立体化学结果是向炔烃中添加HCN以产生（E）产物的结果；总的来说，这些结果构成了制备（E）-2-烷基-3-三烷基甲硅烷基烷基-2-烯醇的简单方法。
• Doyle, M. Michael; Jackson, W. Roy; Perlmutter, Patrick, Australian Journal of Chemistry, 1989, vol. 42, # 11, p. 1907 - 1918
  作者：Doyle, M. Michael、Jackson, W. Roy、Perlmutter, Patrick

  DOI：——

  日期：——
• Inter- and Intramolecular Carbonylative Alkyne–Alkyne Coupling Reaction Mediated by Cobalt Carbonyl Complex
  作者：Takanori Shibata、Koji Yamashita、Kentaro Takagi、Toshihiro Ohta、Kenso Soai

  DOI：10.1016/s0040-4020(00)00902-9

  日期：2000.11

  Inter- and intramolecular carbonylative coupling reactions proceed between alkynes possessing diphenylallylsilyl group mediated by dicobalt carbonyl complex under argon atmosphere. This coupling reaction directly provides various mono- and bicyclic cyclopentadienones in high yields. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Dehydrogenative Silylation of Terminal Alkynes Catalyzed by Ytterbium−Imine Complexes
  作者：Ken Takaki、Masanobu Kurioka、Tohru Kamata、Katsuomi Takehira、Yoshikazu Makioka、Yuzo Fujiwara

  DOI：10.1021/jo981008i

  日期：1998.12.1

  Catalytic dehydrogenative silylation of terminal alkynes with hydrosilanes has been achieved by using divalent Yb-imine complexes; The reaction with mono-, di-, and trihydrosilanes gave the corresponding alkynylsilanes in good yields. alpha,omega-Diynes were similarly silylated at both termini. Thus, oligomers were obtained from the diynes and dihydrosilanes. In addition, it has been found that the imine complexes exhibit catalytic activity for redistribution of the silyl groups of the alkynylsilanes and for Si-Si bond fission of disilanes.