trimethyl-(3,5,5-trimethyl-3-vinylcyclohex-1-enyloxy)silane | 108612-90-4

• 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: trimethyl-(3,5,5-trimethyl-3-vinylcyclohex-1-enyloxy)silane
• 英文别名: 3-ethenyl-3,5,5-trimethyl-1-trimethylsiloxy-1-cyclohexene；(3-Ethenyl-3,5,5-trimethylcyclohexen-1-yl)oxy-trimethylsilane
• CAS: 108612-90-4
• 化学式: C₁₄H₂₆OSi
• 分子量: 238.445
• InChiKey: XREZMYSIQJZDJJ-UHFFFAOYSA-N

物化性质

• 沸点：
  241.2±40.0 °C(Predicted)
• 密度：
  0.87±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trimethyl-(3,5,5-trimethyl-3-vinylcyclohex-1-enyloxy)silane 在 tris(dibenzoylmethano)iron(III) 盐酸 、 samarium diiodide 、 氢溴酸 、 sodium iodide 作用下， 以 四氢呋喃 、 正己烷 、 丙酮 为溶剂， 反应 14.0h， 生成 3,3,5-Trimethylbicyclo<3.2.1>octan-1-ol
  参考文献：
  名称：

  A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction

  摘要：

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.

  DOI：

  10.1021/jo00013a008
• 作为产物：
  描述：

  三甲基氯硅烷 、 异佛尔酮 、 乙烯基溴化镁 在 copper(I) bromide dimethylsulfide complex 六甲基磷酰三胺 作用下， 以 四氢呋喃 为溶剂， 以97%的产率得到trimethyl-(3,5,5-trimethyl-3-vinylcyclohex-1-enyloxy)silane
  参考文献：
  名称：

  Me 3 SiCl / HMPA促进了催化铜试剂的共轭加成。立体异构合成醛烯醇甲硅烷基醚

  摘要：

  在Me 3 SiCl和HMPA存在下，格氏试剂的铜催化共轭加成比常规有机铜试剂的反应收率高得多，并且显示出非常好的区域选择性，立体选择性和化学选择性。

  DOI：

  10.1016/s0040-4039(00)84901-1

文献信息

• Chlorosilane-accelerated conjugate addition of catalytic and stoichiometric organocopper reagents
  作者：Satoshi Matsuzawa、Yoshiaki Horiguchi、Eiichi Nakamura、Isao Kuwajima

  DOI：10.1016/0040-4020(89)80064-x

  日期：1989.1

  Trialkylsilyl chlorides, particularly in combination with hexamethylphosphoramide or 4-dimethylaminopyridine, dramatically accelerates the conjugate addition of catalytic and stoichiometric organocopper reagents onto enones, enals, and enoates, in which very high degrees of stereo- and chemoselectivities were observed.

  三烷基甲硅烷基氯化物，特别是与六甲基磷酰胺或4-二甲基氨基吡啶组合，可显着加速催化和化学计量的有机铜试剂在烯酮，烯醛和烯酸酯上的共轭加成，其中观察到很高的立体和化学选择性。
• Tandem Hydroformylation/Aldol Addition of Silyl Enol Ethers Bearing Remote Olefinic Functionalities
  作者：Christoph Hollmann、Peter Eilbracht

  DOI：10.1016/s0040-4020(00)00071-5

  日期：2000.3

  Rhodium(I) complex catalysed hydroformylation of unsaturated silyl enol ethers leads to products of an intramolecular aldol addition in a one-pot procedure. Thus beta,gamma- or gamma,delta-unsaturated silyl enol ethers undergo tandem hydroformylation/Mukaiyama aldol reaction to form cyclic O-silylated aldol adducts with high selectivity and good yields. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Trimethylsilyl chloride/tetramethylethylenediamine facilitated additions of organocopper reagents (RCu) to enones
  作者：Carl R. Johnson、Thomas J. Marren

  DOI：10.1016/s0040-4039(00)95640-5

  日期：1987.1
• HORIGUCHI YOSHIAKI; MATSUZAWA SATOSHI; NAKAMURA EIICHI; KUWAJIMA ISAO, TETRAHEDRON LETT., 27,(1986) N 34, 4025-4028
  作者：HORIGUCHI YOSHIAKI、 MATSUZAWA SATOSHI、 NAKAMURA EIICHI、 KUWAJIMA ISAO

  DOI：——

  日期：——
• JOHNSON C.; MARREN T. J., TETRAHEDRON LETT., 28,(1987) N 1, 27-30
  作者：JOHNSON C.、 MARREN T. J.

  DOI：——

  日期：——