(E)-(but-2-en-1-yloxy)triisopropylsilane | 223906-17-0

• 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: (E)-(but-2-en-1-yloxy)triisopropylsilane
• 英文别名: [(E)-but-2-enoxy]-tri(propan-2-yl)silane
• CAS: 223906-17-0
• 化学式: C₁₃H₂₈OSi
• 分子量: 228.45
• InChiKey: LWVLISOGWBBLFF-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 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：

  (E)-(but-2-en-1-yloxy)triisopropylsilane 在 正丁基锂 、 氨 、 sodium 、 氯化二乙基铝 作用下， 以 四氢呋喃 、 乙醇 、 叔丁醇 为溶剂， 反应 70.0h， 生成 (+/-)-trans-syn-3-Methyl-1-<(triisopropylsilyl)oxy>-4-hexen-2-ol
  参考文献：
  名称：

  Stereochemistry of the iodocarbonatation of cis- and trans-3-methyl-4-pentene-1,2-diols: the unusual formation of several anti iodo carbonates

  摘要：

  A study on the stereoselective preparation of a series of 3-methyl-4,5-epoxy alcohols as an entry to polypropionates was undertaken. Initially, the opening of cis and trans TIPS-protected 2,3-epoxy butanols by propynyldiethylalane showed an excellent regioselectivity favoring the monoprotected 1,2-diol products. The resulting propargylic alcohols were stereoselectively reduced to the cis and trans 1-[(triisopropylsilyl)oxy]-3-methyl-4-hexen-2-ols. Iodocarbonatation of these four isomeric homoallylic alcohols was carried out and the stereochemistry of the intermediate iodo carbonates established. Interestingly, a complete anti selectivity (>20:1 anti:syn) was observed when both the syn 3-methyl and cis double-bond geometry were present (3b, 10, and 20). The anti relative configuration for all of the iodo carbonates was established by NMR, and that of 5b was confirmed by X-ray crystallography. This study demonstrated that the relative stereochemistry of the hydroxyl and C(3) methyl groups in combination with the cis or trans geometry of the alkene exerts a significant effect on the stereochemical outcome of the iodocarbonatation reaction. Methanolysis of the iodo carbonates produced the desired 3-methyl-4,5-epoxy alcohols. The application of this chemistry to the reiterative synthesis of polypropionates was carried out with epoxy alcohol 4a (anti isomer), producing a new homologated epoxy alcohol, 22, with six contiguous stereocenters in a highly stereoselective manner.

  DOI：

  10.1021/jo00073a027
• 作为产物：
  描述：

  1-triisopropylsiloxy-3-butene 在 2,6-二叔丁基吡啶 、 C₂₆H₄₆IrNO₇P⁽¹⁺⁾*C₃₂H₁₂BF₂₄^(1-) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 48.0h， 生成 (E)-(but-2-en-1-yloxy)triisopropylsilane
  参考文献：
  名称：

  用单一阳离子响应性铱烯烃异构化催化剂选择双键位置

  摘要：

  双键的催化转位有望成为烯烃作为香料，日用化学品和药物的理想途径。然而，选择性获得特定异构体是一个挑战，通常需要针对不同产品独立开发不同的催化剂。在这项工作中，单一的阳离子响应性铱催化剂选择性地产生两种不同的内部烯烃异构体。在不存在盐的情况下，1-丁烯衍生物的单一位置异构化提供具有优异的区域选择性和立体选择性的2-烯烃。Na +存在下相同的催化剂介导两个位置异构化以生成3-烯烃。事实证明，基于aza-18-crown-6醚的铱铱-crown-crown醚催化剂的合成有助于实现阳离子控制的选择性。实验和计算研究指导了机理模型的开发，该机理模型解释了所观察到的对各种官能化的1-丁烯的选择性，从而为基于非共价修饰的催化剂开发策略提供了见识。

  DOI：

  10.1021/jacs.0c11601

文献信息

• Kinetic Resolution in the [2+2] Cycloaddition of Ketenes: An Experimental and Theoretical Study
  作者：Pauline Rullière、Sébastien Carret、Anne Milet、Jean-François Poisson

  DOI：10.1002/chem.201405393

  日期：2015.3.2

  The kinetic resolution of Z and E olefins by [2+2] cycloaddition with ketenes allows the isolation of pure E olefin, as well as the synthesis of pure cis‐cyclobutanones, starting from Z/E mixtures. A computational rationale for this kinetic difference is reported. The obtained difference of energy of activation matches with the experimental results.

  Z和E烯烃通过与烯酮的[2 + 2]环加成反应的动力学拆分，可以从Z / E混合物开始分离纯E烯烃，以及合成纯顺式-环丁烷酮。报道了该动力学差异的计算原理。所获得的活化能差与实验结果相符。
• Ligand-controlled cobalt-catalyzed remote hydroboration and alkene isomerization of allylic siloxanes
  作者：Pei Zhao、Jiaxin Huang、Jie Li、Kezhuo Zhang、Wen Yang、Wanxiang Zhao

  DOI：10.1039/d1cc05964e

  日期：——

  The Co-catalyzed remote hydroboration and alkene isomerization of allylic siloxanes were realized by a ligand-controlled strategy. The remote hydroboration with dcype provided borylethers, while xantphos favored the formation of silyl enol ethers.

  烯丙基硅氧烷的共催化远程硼氢化和烯烃异构化是通过配体控制的策略实现的。用 dcype 进行远程硼氢化反应提供硼醚，而 xantphos 有利于形成甲硅烷基烯醇醚。
• A Selenium Catalyzed Epoxidation in Perfluorinated Solvents with Hydrogen Peroxide
  作者：Bodo Betzemeier、Frédéric Lhermitte、Paul Knochel

  DOI：10.1055/s-1999-2630

  日期：1999.4

  The readily prepared 2,4-bisperfluorooctylphenyl butylselenide catalyzes the epoxidation of various olefins with hydrogen peroxide in a fluorous biphasic system. The catalyst is selectively soluble in perfluorinated solvents and can easily be recovered simply by phase separation. Furthermore, the catalyst can be reused several times without a decrease of yield and an increase of reaction time.

  readily prepared 2,4-bisperfluorooctylphenyl butylselenide 催化了在氟相双相体系中用过氧化氢对各种烯烃进行的环氧化反应。该催化剂在全氟化溶剂中具有选择性的溶解性，并且通过相分离可以轻松回收。此外，该催化剂可以重复使用多次，而不会降低产率或延长反应时间。
• Selecting Double Bond Positions with a Single Cation-Responsive Iridium Olefin Isomerization Catalyst
  作者：Andrew M. Camp、Matthew R. Kita、P. Thomas Blackburn、Henry M. Dodge、Chun-Hsing Chen、Alexander J. M. Miller

  DOI：10.1021/jacs.0c11601

  日期：2021.2.24

  stereoselectivity. The same catalyst, in the presence of Na+, mediates two positional isomerizations to produce 3-alkenes. The synthesis of new iridium pincer-crown ether catalysts based on an aza-18-crown-6 ether proved instrumental in achieving cation-controlled selectivity. Experimental and computational studies guided the development of a mechanistic model that explains the observed selectivity for various functionalized

  双键的催化转位有望成为烯烃作为香料，日用化学品和药物的理想途径。然而，选择性获得特定异构体是一个挑战，通常需要针对不同产品独立开发不同的催化剂。在这项工作中，单一的阳离子响应性铱催化剂选择性地产生两种不同的内部烯烃异构体。在不存在盐的情况下，1-丁烯衍生物的单一位置异构化提供具有优异的区域选择性和立体选择性的2-烯烃。Na +存在下相同的催化剂介导两个位置异构化以生成3-烯烃。事实证明，基于aza-18-crown-6醚的铱铱-crown-crown醚催化剂的合成有助于实现阳离子控制的选择性。实验和计算研究指导了机理模型的开发，该机理模型解释了所观察到的对各种官能化的1-丁烯的选择性，从而为基于非共价修饰的催化剂开发策略提供了见识。
• Stereochemistry of the iodocarbonatation of cis- and trans-3-methyl-4-pentene-1,2-diols: the unusual formation of several anti iodo carbonates
  作者：Raymond Tirado、Jose A. Prieto

  DOI：10.1021/jo00073a027

  日期：1993.10

  A study on the stereoselective preparation of a series of 3-methyl-4,5-epoxy alcohols as an entry to polypropionates was undertaken. Initially, the opening of cis and trans TIPS-protected 2,3-epoxy butanols by propynyldiethylalane showed an excellent regioselectivity favoring the monoprotected 1,2-diol products. The resulting propargylic alcohols were stereoselectively reduced to the cis and trans 1-[(triisopropylsilyl)oxy]-3-methyl-4-hexen-2-ols. Iodocarbonatation of these four isomeric homoallylic alcohols was carried out and the stereochemistry of the intermediate iodo carbonates established. Interestingly, a complete anti selectivity (>20:1 anti:syn) was observed when both the syn 3-methyl and cis double-bond geometry were present (3b, 10, and 20). The anti relative configuration for all of the iodo carbonates was established by NMR, and that of 5b was confirmed by X-ray crystallography. This study demonstrated that the relative stereochemistry of the hydroxyl and C(3) methyl groups in combination with the cis or trans geometry of the alkene exerts a significant effect on the stereochemical outcome of the iodocarbonatation reaction. Methanolysis of the iodo carbonates produced the desired 3-methyl-4,5-epoxy alcohols. The application of this chemistry to the reiterative synthesis of polypropionates was carried out with epoxy alcohol 4a (anti isomer), producing a new homologated epoxy alcohol, 22, with six contiguous stereocenters in a highly stereoselective manner.