1-(三甲基甲硅烷基)丁-3-烯-2-基乙酸酯 | 134600-35-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 1-(三甲基甲硅烷基)丁-3-烯-2-基乙酸酯
• 英文名称: 2-Propen-1-ol, 2-(trimethylsilyl)methyl-, acetate
• 英文别名: 1-trimethylsilylbut-3-en-2-yl acetate
• CAS: 134600-35-4
• 化学式: C₉H₁₈O₂Si
• 分子量: 186.326
• InChiKey: FTZACGIEIMCZII-UHFFFAOYSA-N

物化性质

• 沸点：
  202.1±20.0 °C(Predicted)
• 密度：
  0.879±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.44
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(三甲基甲硅烷基)丁-3-烯-2-基乙酸酯 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.58h， 生成 (2E,7E)-5,5-dimethyl-9-(trimethylsilanyl)nona-2,7-dien-4-one
  参考文献：
  名称：

  Regioselective Catalytic Transformations Involving β-Silyl-Substituted (η³-Allyl)palladium Complexes:  An Efficient Route to Functionalized Allylsilanes

  摘要：

  Various alkyl derivatives of 1-(trimethylsilanyl)but-3-en-2-ol acetate (1a-e) undergo regioselective palladium-catalyzed nucleophilic substitution via beta-silyl-substituted (eta(3)-allyl)palladium intermediates. With external nucleophiles, such as malonates and enolates, the nucleophilic substitution occurs with complete allylic rearrangement, providing functionalized allylsilanes as building blocks of high synthetic potential. Internal nucleophiles, such as disilanes and NaBPh4, afford bisallylic disilanes and (allylsilyl)benzene derivatives with good regioselectivity. For both types of nucleophiles, the double bond geometry of the resulting allylsilane is selectively traits. The beta-silyl-substituted (eta(3)-allyl)palladium intermediates of the reaction were also isolated. The H-1 NMR studies indicate selective formation of the syn-isomer of the key (eta(3)-allyl)palladium intermediates, which explains the high trans-selectivity of the double bond formation in the allylsilane products. According to the C-13 NMR studies, the beta-silyl functionality exerts deshielding effects on the nearest allylic terminal carbon (C3), which can be ascribed to hyperconjugative interactions between the silyl functionality and the allylpalladium moiety. It was concluded that, together with the steric effects of the silyl group, these electronic interactions are responsible for the high regioselectivity of the nucleophilic attack in the catalytic process.

  DOI：

  10.1021/jo991172l

文献信息

• Palladium Pincer Complex Catalyzed Substitution of Vinyl Cyclopropanes, Vinyl Aziridines, and Allyl Acetates with Tetrahydroxydiboron. An Efficient Route to Functionalized Allylboronic Acids and Potassium Trifluoro(allyl)borates
  作者：Sara Sebelius、Vilhelm J. Olsson、Kálmán J. Szabó

  DOI：10.1021/ja052885q

  日期：2005.8.1

  Palladium-catalyzed boronation of vinyl cyclopropane, vinyl aziridine, and allyl acetate substrates could be accomplished using tetrahydroxydiboron reagent in the presence of SeCSe pincer complex catalyst 1a. These reactions result in allyl boronic acids, which were converted to synthetically useful trifluoro(allyl)borates or allyl boronates. The catalytic transformations proceed under mild and neutral

  钯催化的乙烯基环丙烷、乙烯基氮丙啶和乙酸烯丙酯底物的硼化可以在 SeCSe 钳形配合物催化剂 1a 存在下使用四羟基二硼试剂完成。这些反应产生烯丙基硼酸，其被转化为合成有用的三氟（烯丙基）硼酸酯或烯丙基硼酸酯。催化转化在温和和中性条件下进行，因此可以耐受许多官能团 Br、COOEt、ArSO2(NH)、OAc 和 SiRMe2。所提出的方法的选择性非常高，提供了包含反式双键的线性产品。
• Single-pot triple catalytic transformations based on coupling of in situ generated allyl boronates with in situ hydrolyzed acetals
  作者：Nicklas Selander、Kálmán J. Szabó

  DOI：10.1039/b804920c

  日期：——

  In situ hydrolyzed acetals were coupled with in situ generated allyl boronates in a one-pot procedure, affording regio- and stereodefined homoallyl alcohols, epoxides and amino alcohols.

  以一锅法将原位水解的乙缩醛与原位生成的硼酸烯丙酯偶联，得到区域和立体定义的均烯丙基醇，环氧化物和氨基醇。
• Synthesis of Stereodefined Substituted Cycloalkenes by a One-Pot Catalytic Boronation-Allylation-Metathesis Sequence
  作者：Nicklas Selander、Kálmán J. Szabó

  DOI：10.1002/adsc.200800324

  日期：2008.9.5

  stereoselectivities. The presented procedure has a broad synthetic scope and high functional group tolerance, which allows the synthesis of bicyclic lactone and spirane skeletons and various substitution patterns including hydroxy, silyl, vinyl, allyl, and sulfonyl groups. The studied catalytic one-pot reactions involve up to three individual processes performed by up to four acid- and transition metal-catalyzed

  通过将烯丙基醇和其他烯丙基前体与不饱和醛偶联来制备立体确定的环己烯和环戊烯衍生物。这些反应基于多催化一锅法，其中包括钯钳复合物催化的硼化，烯丙基化和闭环易位反应。该反应序列可以以操作简单的程序进行，从而以高的总收率以及优异的区域选择性和立体选择性提供环烯烃产物。所提出的方法具有广泛的合成范围和高官能团耐受性，其允许合成双环内酯和螺环骨架以及各种取代模式，包括羟基，甲硅烷基，乙烯基，烯丙基和磺酰基。
• Carbopalladation of functionalized allenes : regioselectivity of the reaction of carbonucleophiles with the intermediate π-allyl palladium complexes.
  作者：Nathalie Chaptal、Véronique Colovray-Gotteland、Cyrille Grandjean、Bernard Cazes、Jacques Goré

  DOI：10.1016/s0040-4039(00)74332-2

  日期：1991.4

  Carbopalladation of functionalized allenes leads to pi-allyl palladium complexes, the regiochemistry of which towards carbonucleophiles has been studied : a methoxy group has been demonstrated to reverse the classical regioselectivity and to allow the formation of the more substituted product.
• Regioselective Catalytic Transformations Involving β-Silyl-Substituted (η³-Allyl)palladium Complexes:  An Efficient Route to Functionalized Allylsilanes
  作者：István Macsári、Eike Hupe、Kálmán J. Szabó

  DOI：10.1021/jo991172l

  日期：1999.12.1

  Various alkyl derivatives of 1-(trimethylsilanyl)but-3-en-2-ol acetate (1a-e) undergo regioselective palladium-catalyzed nucleophilic substitution via beta-silyl-substituted (eta(3)-allyl)palladium intermediates. With external nucleophiles, such as malonates and enolates, the nucleophilic substitution occurs with complete allylic rearrangement, providing functionalized allylsilanes as building blocks of high synthetic potential. Internal nucleophiles, such as disilanes and NaBPh4, afford bisallylic disilanes and (allylsilyl)benzene derivatives with good regioselectivity. For both types of nucleophiles, the double bond geometry of the resulting allylsilane is selectively traits. The beta-silyl-substituted (eta(3)-allyl)palladium intermediates of the reaction were also isolated. The H-1 NMR studies indicate selective formation of the syn-isomer of the key (eta(3)-allyl)palladium intermediates, which explains the high trans-selectivity of the double bond formation in the allylsilane products. According to the C-13 NMR studies, the beta-silyl functionality exerts deshielding effects on the nearest allylic terminal carbon (C3), which can be ascribed to hyperconjugative interactions between the silyl functionality and the allylpalladium moiety. It was concluded that, together with the steric effects of the silyl group, these electronic interactions are responsible for the high regioselectivity of the nucleophilic attack in the catalytic process.