1-trimethylsilyl-cis-cis-cyclo-octa-1,5-diene | 79643-81-5

• 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
• 英文名称: 1-trimethylsilyl-cis-cis-cyclo-octa-1,5-diene
• 英文别名: 1-trimethylsilyl-1,5-cyclooctadiene；[(1E,5Z)-cycloocta-1,5-dien-1-yl]-trimethylsilane
• CAS: 79643-81-5
• 化学式: C₁₁H₂₀Si
• 分子量: 180.365
• InChiKey: IMRMHBFCZWHPOV-JWPKELMXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.92
• 重原子数：
  12.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1-trimethylsilyl-cis-cis-cyclo-octa-1,5-diene 在 palladium dichloride 作用下， 以 乙醇 为溶剂， 生成 1,5-cis,cis-cyclooctadiene 、 顺-环辛烯
  参考文献：
  名称：

  Trimethylsilylcyclooctadiene-transition metal complexes: metal-catalysed protodesilylation of cyclic vinylsilanes, and transfer hydrogenation promoted by the displaced silyl group

  摘要：

  Complexes of 1-trimethylsilyl-1,5-cyclooctadiene (TMS-COD, 2) with Ag(I), Rh(I), Pd(II) and Pt(II) have been prepared and characterised. The distortion in their structures in comparison with the near symmetrical structures of the corresponding 1,5-cyclooctadiene (COD, 1) complexes, which is obviously attributable to the presence of vinylic SiMe3 group, is clearly indicated by their H-1 and C-13 NMR spectral characteristics. The silver complex is somewhat unstable, but the other complexes are quite stable. An unstable Cu(I) complex that could not be satisfactorily characterised was also obtained. If appropriate conditions for the preparation of Rh and Pd complexes are not maintained, desilylation occurs, accompanied by reduction of COD to cyclooctene by transfer of hydrogen from the solvent alcohol. The displaced silicon containing moiety seems to enhance the transfer hydrogenation. Attempts to prepare Ru(II) complex resulted in the formation of a complex of desilylated diene (Ru(II)-COD).

  DOI：

  10.1016/0022-328x(92)83272-j
• 作为产物：
  描述：

  三甲基氯硅烷 、 1-Brom-1,5-cyclooctadien 在 sodium 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 以87%的产率得到1-trimethylsilyl-cis-cis-cyclo-octa-1,5-diene
  参考文献：
  名称：

  Trimethylsilylcyclooctadiene-transition metal complexes: metal-catalysed protodesilylation of cyclic vinylsilanes, and transfer hydrogenation promoted by the displaced silyl group

  摘要：

  Complexes of 1-trimethylsilyl-1,5-cyclooctadiene (TMS-COD, 2) with Ag(I), Rh(I), Pd(II) and Pt(II) have been prepared and characterised. The distortion in their structures in comparison with the near symmetrical structures of the corresponding 1,5-cyclooctadiene (COD, 1) complexes, which is obviously attributable to the presence of vinylic SiMe3 group, is clearly indicated by their H-1 and C-13 NMR spectral characteristics. The silver complex is somewhat unstable, but the other complexes are quite stable. An unstable Cu(I) complex that could not be satisfactorily characterised was also obtained. If appropriate conditions for the preparation of Rh and Pd complexes are not maintained, desilylation occurs, accompanied by reduction of COD to cyclooctene by transfer of hydrogen from the solvent alcohol. The displaced silicon containing moiety seems to enhance the transfer hydrogenation. Attempts to prepare Ru(II) complex resulted in the formation of a complex of desilylated diene (Ru(II)-COD).

  DOI：

  10.1016/0022-328x(92)83272-j

文献信息

• Some epoxide ring-opening reactions of αβ-epoxysilanes
  作者：Anthony P. Davis、Gwyneth J. Hughes、Peter R. Lowndes、Catherine M. Robbins、Elizabeth J. Thomas、Gordon H. Whitham

  DOI：10.1039/p19810001934

  日期：——

  Epoxide ring-opening of 1,2-epoxy-1-trimethylsilylcyclohexane (3) has given a range of the 2-substituted 2-trimethylsilylcyclohexanols (4; X = H, OH, OMe, OCH2CHCH2, Br, I, SCN) in which attack by nucleophile has occurred at the carbon α to silicon. The products (4) have been transformed into a number of functionalised silanes, including the silyl-episulphide (9). Other epoxides which have been less

  1,2-环氧-1-三甲基甲硅烷基环己烷（3）的环氧开环给出了一系列2-取代的2-三甲基甲硅烷基环己醇（4; X = H，OH，OMe，OCH 2 CH CH 2，Br，I， SCN），其中亲核试剂的攻击发生在碳原子对硅的α处。产物（4）已被转化为许多官能化的硅烷，包括甲硅烷基-环二硫化物（9）。尚未进行广泛研究的其他环氧化物是结构偏倚的环氧硅烷（10）和（11），八元环环氧硅烷（17）和（21）以及两种立体异构体2,3-环氧-3-三甲基甲硅烷基戊烷（26）和（29）。用H +处理后获得环氧开环加合物除化合物（17）以外，所有情况下均为-MeOH，其中双环醇（18）通过环过环反应形成。