(E)-1-[dimethyl(phenyl)silyl]-4-phenylbut-2-ene | 141543-30-8

• 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)-1-[dimethyl(phenyl)silyl]-4-phenylbut-2-ene
• 英文别名: dimethyl-phenyl-[(E)-4-phenylbut-2-enyl]silane
• CAS: 141543-30-8
• 化学式: C₁₈H₂₂Si
• 分子量: 266.458
• InChiKey: XKAZYNDINCRLSN-MDZDMXLPSA-N

物化性质

• 沸点：
  371.6±31.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (E)-1-[dimethyl(phenyl)silyl]-4-phenylbut-2-ene 在 三甲基铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 16.0h， 生成 4-苯丁酸甲酯
  参考文献：
  名称：

  The Regiochemistry of the Protodesilylation of Some Cyclopropylmethylsilanes Derived from Allylsilanes

  摘要：

  烯丙基硅烷的 Simmons-Smith 型甲烯化反应，然后是原代硅烷化反应，可用于实现甲基基团对硅烷基团的 SE2′置换。环丙基甲基硅烷 11、17、20 和 23 亚甲基碳上的质子化具有良好的区域选择性，但形成环丙基甲基硅烷 26 的立体选择性较低，而且不能进行干净的原代甲硅烷基化，因此该方法的用途有限。

  DOI：

  10.1055/s-1992-34186
• 作为产物：
  描述：

  1-苯基-3-丁烯-2-醇 、 dimethyl(phenyl)silyllithium 在 氯化亚砜 作用下， 生成 (E)-1-[dimethyl(phenyl)silyl]-4-phenylbut-2-ene
  参考文献：
  名称：

  The Regiochemistry of the Protodesilylation of Some Cyclopropylmethylsilanes Derived from Allylsilanes

  摘要：

  烯丙基硅烷的 Simmons-Smith 型甲烯化反应，然后是原代硅烷化反应，可用于实现甲基基团对硅烷基团的 SE2′置换。环丙基甲基硅烷 11、17、20 和 23 亚甲基碳上的质子化具有良好的区域选择性，但形成环丙基甲基硅烷 26 的立体选择性较低，而且不能进行干净的原代甲硅烷基化，因此该方法的用途有限。

  DOI：

  10.1055/s-1992-34186

文献信息

• 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.
• Cp₂TiCl₂-Catalyzed Regio- and Chemoselective One-Step Synthesis of γ-Substituted Allylsilanes from Terminal Alkenes Using Dianion-Type Zincate (SiSiNOL-Zn-ate)
  作者：Shinji Nakamura、Masanobu Uchiyama、Tomohiko Ohwada

  DOI：10.1021/ja0541074

  日期：2005.9.28

  A regio-/chemoselective silylation reaction of various functionalized terminal alkenes in the presence of titanocene dichloride, based on a newly designed dianion-type zincate, was developed. The present silylation of terminal alkenes is a powerful tool for the one-pot generation of regiocontrolled functionalized allysilanes, which are available for various transformation reactions, such as hydroxyalkylation, epoxidation, and hydroboration.
• 1,4-Carbosilylation of 1,3-Dienes via Palladium Catalyzed Three-Component Coupling Reaction
  作者：Yasushi Obora、Yasushi Tsuji、Takashi Kawamura

  DOI：10.1021/ja00144a005

  日期：1995.10

  Three-component coupling reaction of acid chlorides, organodisilanes, and 1,3-dienes achieves 1,4-carbosilylation of the 1,3-dienes to afford allylic silanes as the product. Bis(dibenzylideneacetone)palladium, a naked Pd(0) complex without donating ligand, showed high catalytic activity. A carbon and a silicon substituent are introduced at 1- and 4-positions of the 1,3-dienes regio- and stereoselectively with concomitant decarbonylation of the acid chlorides. A wide variety of allylic silanes are synthesized in high yields from these easily accessible substrates. On the other hand, a bully acid chloride such as adamantane-1-carboxylic acid chloride did not undergo the decarbonylation reaction but afforded allylic silanes containing acyl functionality. In all these reactions, transmetalation of the disilanes with eta(3)-allylchloropalladium intermediates might be a critical step in the catalytic cycle. As a model reaction for the transmetalation, reaction of di-mu-chlorobis[(1,2,3-eta)-4-phenyl-2-butenyl]dipalladium with disilanes was carried out. Although intermediate eta(3)-allylsilylpalladium species could not be detected, the corresponding allylic silanes, silyl chlorides, and Pd(0) metal were formed during the reaction. Furthermore, a similar three-component coupling reaction using aryl iodides, organosilylstannanes, and dienes also proceeded. However, the selectivity and the yield decreased considerably.
• Desulfurizative silation, germation, and stannation of thioacetals and their analogues utilizing titanocene(II)
  作者：Takeshi Takeda、Naoki Nozaki、Tooru Fujiwara

  DOI：10.1016/s0040-4039(98)00524-3

  日期：1998.5

  Desulfurization of thioacetals with the low valent titanium species Cp2Ti[P(OEt)(3)](2) in the presence of trialkylsilanes afforded the corresponding tetraalkylsilanes. Allylsilanes were obtained regioselectively using beta,gamma-unsaturated thioacetals or 1,3-bis(phenylthio)alk-1-enes as starting materials. The similar titanocene(II)-promoted reactions of these organosulfur compounds with triethylgermane and tributylstannane gave tetraorganogermanes and stannanes, respectively. (C) 1998 Elsevier Science Ltd. All rights reserved.
• The Regiochemistry of the Protodesilylation of Some Cyclopropylmethylsilanes Derived from Allylsilanes
  作者：Ian Fleming、Philip E. J. Sanderson、Nicholas K. Terrett

  DOI：10.1055/s-1992-34186

  日期：——

  Simmons-Smith type methylenation of allylsilanes, followed by protodesilylation, can be used to achieve overall the SE2′ replacement of the silyl group by a methyl group. The regioselectivity is good for protonation on the methylene carbon of the cyclopropylmethylsilanes 11, 17, 20 and 23, but the low stereoselectivity in the formation of the cyclopropylmethylsilane 26 and its failure to undergo clean protodesilylation make the method of limited use.

  烯丙基硅烷的 Simmons-Smith 型甲烯化反应，然后是原代硅烷化反应，可用于实现甲基基团对硅烷基团的 SE2′置换。环丙基甲基硅烷 11、17、20 和 23 亚甲基碳上的质子化具有良好的区域选择性，但形成环丙基甲基硅烷 26 的立体选择性较低，而且不能进行干净的原代甲硅烷基化，因此该方法的用途有限。