2-methyl-4-phenyl-4-trimethylsiloxy-1-butene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-methyl-4-phenyl-4-trimethylsiloxy-1-butene
• 英文别名: Trimethyl-(3-methyl-1-phenylbut-3-enoxy)silane；trimethyl-(3-methyl-1-phenylbut-3-enoxy)silane
• 化学式: C₁₄H₂₂OSi
• 分子量: 234.414
• InChiKey: ADEIEYABOQWHNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.55
• 重原子数：
  16
• 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：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-4-phenyl-4-trimethylsiloxy-1-butene 在 盐酸 、 水 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成 3-methyl-1-phenylbut-3-en-1-ol
  参考文献：
  名称：

  Mesoporous aluminosilicate-catalyzed allylation of carbonyl compounds and acetals

  摘要：

  A mesoporous aluminosilicate (Al-MCM-41) was found to be an effective heterogeneous catalyst for the reaction of both carbonyl compounds and acetals with allylsilanes to afford the corresponding homoallyl silyl ethers and homoallyl alkyl ethers, respectively. Both the mesoporous structure and the presence of aluminum moiety were indispensable for the high catalytic activity of Al-MCM-41. Moreover, Al-MCM-41 could catalyze the reaction of acetals chemoselectively in the presence of the corresponding carbonyl compounds. The solid acid catalyst Al-MCM-41 could be recovered easily by filtration and could be reused three times without a significant loss of catalytic activity. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.01.055
• 作为产物：
  描述：

  异丁烯基三甲基硅烷 、 苯甲醛 在 3,3’-bis[3,5-bis(perfluoropropan-2-yl)phenyl]-1,1’-binaphthalene-2,2’-sulfonimide 作用下， 以 乙腈 为溶剂， 生成 2-methyl-4-phenyl-4-trimethylsiloxy-1-butene
  参考文献：
  名称：

  不对称抗衡阴离子导向的细森-樱井反应

  摘要：

  抗衡阴离子的控制可使用易于处理的二磺酰亚胺预催化剂使对映体选择性有机路易斯酸催化（杂）芳族醛和烯丙基硅烷的Hosomi-Sakurai反应（参见方案）。该系统成功的关键在于将通常不希望的甲硅烷基离子催化转化为所需的催化方案，并将阳离子与对映体纯的二磺酰亚胺阴离子配对，从而应用了不对称抗衡阴离子导向催化的概念。

  DOI：

  10.1002/chem.201203623

文献信息

• Homogeneous catalysis. Use of the [TiCp2(CF3SO3)2] catalyst for the sakurai reaction of allylic silanes with orthoesters, acetals, ketals and carbonyl compounds.
  作者：T. Keith Hollis、N.P. Robinson、John Whelan、B. Bosnich

  DOI：10.1016/s0040-4039(00)79336-1

  日期：1993.7

  The effectiveness of the [TiCp2(CF3SO3)2] catalyst for the Sakurai reaction has been explored for a variety of allylic silanes reacting with orthoesters, acetals, ketals, aldehydes and ketones.

  对于与原酸酯，缩醛，缩酮，醛和酮反应的各种烯丙基硅烷，已经探索了[TiCp 2（CF 3 SO 3）2 ]催化剂在樱井反应中的有效性。
• Homogeneous Catalysis. Mechanisms of the Catalytic Mukaiyama Aldol and Sakurai Allylation Reactions
  作者：T. Keith Hollis、B. Bosnich

  DOI：10.1021/ja00121a015

  日期：1995.4

  The mechanisms of a number of Mukaiyama aldol and Sakurai allylation reactions catalyzed by the Lewis acids [Ti(Cp)(2)(OTf)(2)], Ph(3)COTf, and Ph(3)CClO(4) have been investigated. It is found that hydrolysis of the Lewis acid by trace amounts of water in the solvent can lead to the formation of acid. The acid then reacts with the silyl enol ether or allylic silane to generate Me(3)SiOTf or Me(3)SiClO(4), both of which are powerful catalysts for these reactions. Dehydration of the solvent or addition of a hindered base to quench the acid does not necessarily prevent the formation of these silyl catalysts. In the case of the [Ti(Cp)(2)(OTf)(2)] Lewis acid, Me(3)SiOTf is generated as a consequence of the mechanism, and it is shown that all of the catalysis proceeds by the Me(3)SiOTf species and that [Ti(Cp)(2)(OTf)(2)] acts only as an initiator for the production of Me(3)SiOTf. For the case of the presumed Ph(3)COTf catalyst, the Mukaiyama aldol reaction proceeds exclusively by the Me(3)SiOTf catalyst and Ph(3)COTf is neither an initiator nor a catalyst. It generates Me(3)SiOTf by hydrolysis. It is shown that the rate and stereoselectivity of Me(3)SiOTf catalysis depend on the concentration of triflate ions. The rate slows and the selectivity switches with an increase in triflate concentration. The rate of Sakurai catalysis of allylsilane with an acetal using Ph(3)CClO(4) can be quantitatively accounted for by invoking only Me(3)SiClO(4) catalysis. The Me(3)SiClO(4) can be generated by hydrolysis, but when this is suppressed, Me(3)SiClO(4) can be formed by allylation of Ph(3)CClO(4). It is suggested that many of the reported catalysts may only be agents for the production of the real catalysts, namely, Me(3)SiX species. The characteristics of Lewis acids which may obviate the intrusion of Me(3)SiX catalysis are outlined.
• Mesoporous aluminosilicate-catalyzed allylation of carbonyl compounds and acetals
  作者：Suguru Ito、Akira Hayashi、Hirotomo Komai、Hitoshi Yamaguchi、Yoshihiro Kubota、Masatoshi Asami

  DOI：10.1016/j.tet.2011.01.055

  日期：2011.3

  A mesoporous aluminosilicate (Al-MCM-41) was found to be an effective heterogeneous catalyst for the reaction of both carbonyl compounds and acetals with allylsilanes to afford the corresponding homoallyl silyl ethers and homoallyl alkyl ethers, respectively. Both the mesoporous structure and the presence of aluminum moiety were indispensable for the high catalytic activity of Al-MCM-41. Moreover, Al-MCM-41 could catalyze the reaction of acetals chemoselectively in the presence of the corresponding carbonyl compounds. The solid acid catalyst Al-MCM-41 could be recovered easily by filtration and could be reused three times without a significant loss of catalytic activity. (C) 2011 Elsevier Ltd. All rights reserved.
• Asymmetric Counteranion-Directed Catalytic Hosomi-Sakurai Reaction
  作者：Manuel Mahlau、Pilar García-García、Benjamin List

  DOI：10.1002/chem.201203623

  日期：2012.12.14

  Lewis acid catalyzed Hosomi–Sakurai reaction of (hetero)aromatic aldehydes and allylsilanes using an easily handled disulfonimide precatalyst (see scheme). The key to the success of this system is to turn the usually undesired silylium ion catalysis into the desired catalytic regime and pair the cation with an enantiopure disulfonimide anion, thereby applying the concept of asymmetric counteranion‐directed

  抗衡阴离子的控制可使用易于处理的二磺酰亚胺预催化剂使对映体选择性有机路易斯酸催化（杂）芳族醛和烯丙基硅烷的Hosomi-Sakurai反应（参见方案）。该系统成功的关键在于将通常不希望的甲硅烷基离子催化转化为所需的催化方案，并将阳离子与对映体纯的二磺酰亚胺阴离子配对，从而应用了不对称抗衡阴离子导向催化的概念。