Dimethyl-(2-methylidenebut-3-enyl)-phenylsilane | 187800-99-3

• 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: Dimethyl-(2-methylidenebut-3-enyl)-phenylsilane
• CAS: 187800-99-3
• 化学式: C₁₃H₁₈Si
• 分子量: 202.371
• InChiKey: FPDKFSSUWAXBLS-UHFFFAOYSA-N

物化性质

• 沸点：
  264.3±19.0 °C(Predicted)
• 密度：
  0.87±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.34
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 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：

  Dimethyl-(2-methylidenebut-3-enyl)-phenylsilane 在 三氯化铝 、 二异丁基氢化铝 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 4.25h， 生成 2-甲基-6-亚甲基-2,7-辛二烯-4-醇
  参考文献：
  名称：

  Allylsilane-Vinylcopper Reagents: Palladium-Mediated Coupling with Alkenyl Halides. Synthesis and Photochemical [2 + 2] Cyclization of (±)-Ipsdienol

  摘要：

  苯基二甲基硅基铜与 1,2-丙二烯反应，然后在 Pd0 催化下将生成的铜中间体与烯烃卤化物偶联，就能以高产率生成含烯丙硅烷的二烯。与乙烯基溴偶联可得到 2-苯基二甲基硅甲基丁-1,3-二烯，它是合成(±)-Ipsenol 和(±)-Ipsdienol 的异戊烯基结构单元，而 (±)-Ipsenol 和 (±)-Ipsdienol 是 Ips 树皮甲虫的聚集信息素。此外，还研究了 Ipsdienol 的光化学 [2 + 2] 环化过程。

  DOI：

  10.1055/s-2001-14589
• 作为产物：
  描述：

  magnesium,methanidyl-dimethyl-phenylsilane,chloride 、 2-氯-1.3-丁二烯 在 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 作用下， 以 乙醚 为溶剂， 反应 5.0h， 以97%的产率得到Dimethyl-(2-methylidenebut-3-enyl)-phenylsilane
  参考文献：
  名称：

  Noncascade Tandem Transformations Involving Allylic Silanes. 1. Pericyclic and Ionic Reactions Combined into “One-Pot” Sequences

  摘要：

  DOI：

  10.1021/jo962025f

文献信息

• Pd-catalyzed cross-coupling of allylsilane-vinylcopper species with aryl and vinyl halides: the first total synthesis of (−)-nomadone
  作者：Francisco J. Pulido、Asunción Barbero、Carlos García

  DOI：10.1016/j.tet.2009.01.118

  日期：2009.7

  The reaction of allene with a lower order silylcuprate 3 leads to an allylsilane-vinylcopper intermediate 4, which undergoes palladium-catalyzed cross-coupling reaction with both vinyl and aryl halides. The influence of several factors such as the nature of the transition metal used as catalyst, the temperature of the reaction, and the order of addition are studied. This simple methodology allows the

  丙二烯与低级甲硅烷基铜酸酯3的反应生成烯丙基硅烷-乙烯基铜中间体4，该中间体进行钯催化的与乙烯基卤化物和芳基卤化物的交叉偶联反应。研究了几种因素的影响，例如用作催化剂的过渡金属的性质，反应温度和添加顺序。这种简单的方法可以一步合成异戊二烯基硅烷，可以方便地将其与不同的异戊二烯醛偶联，得到几种无环的天然萜烯。因此，我们能够从艾伦中分两步合成天然单萜（±）-ipsdienol和（±）-ipsenol，这是树皮甲虫Ips paraconfusus的聚集信息素的主要成分。。另一方面，异戊二烯基硅烷7与天然单萜（S）-香茅醛的烯丙基封端反应生成中间体，该中间体很容易在两个几乎定量的步骤中转化为天然倍半萜（-）-Nomadone。游牧民倍半萜是诺曼达蜜蜂的头腺分泌物的组成部分。据我们所知，这是第一个报道的（-）-游豆酮的全合成。
• Tandem Transformations Involving Allylic Silanes. 2. Highly Diastereoselective Substitutions Involving [(Trialkylsilyl)methyl]cyclohexene Derivatives with Aldehydes. Synthetic Studies on the Problem of Lewis Acid-Promoted Protodesilylation and Enolization
  作者：Michael G. Organ、Derick D. Winkle、John Huffmann

  DOI：10.1021/jo970821v

  日期：1997.8.1

  Diels-Alder cycloaddition of 2-[(trialkylsilyl)methyl]-1,3-butadienes with a variety of dienophiles and substitution reactions between these allylsilane-containing adducts and aldehyde or acid chloride electrophiles have been combined into ''tandem sequential reactions.'' These tandem sequences proceed with equal or greater yield (50-80%) than the reactions performed separately with no decrease in regio- or stereoselectivity. The sequence produces cyclic compounds with three or four stereogenic centers with good to excellent diastereoselectivity from three simple, noncyclic, and achiral reaction partners. Unprecedented levels of diastereoselectivity (de > 93%) have been achieved in allylic substitution reactions involving substituted [(trialkylsilyl)methyl]cyclohexene derivatives with aldehyde electrophiles. During the course of these studies, protodesilylation of allylsilanes has been investigated in detail, and a cocatalyst system of TiCl4 and Me2AlCl has been developed that has eliminated silicon loss in the substitution reactions studied. Lewis acid-promoted enolization of ester and ketone substrates with chiral centers adjacent to the carbonyl moiety has been studied also. It has been shown that this event in our studies occurs primarily during catalyst quench. This isomerization is prevented by quenching the catalyst with a Lewis base, such as methanol or triethylamine, prior to aqueous workup.
• Allylsilane-Vinylcopper Reagents: Palladium-Mediated Coupling with Alkenyl Halides. Synthesis and Photochemical [2 + 2] Cyclization of (±)-Ipsdienol
  作者：Asunción Barbero、Carlos García、Francisco J. Pulido

  DOI：10.1055/s-2001-14589

  日期：——

  Reaction of phenyldimethylsilyl-copper with 1,2-propadiene followed by Pd0 catalyzed coupling of the resulting copper intermediate with alkenyl halides affords allylsilane-containing dienes in high yield. Coupling with vinyl bromide gives 2-phenyldimethylsilylmethylbuta-1,3-diene which is an isoprenyl building block for the synthesis of (±)-Ipsenol and (±)-Ipsdienol, the aggregation pheromones of the Ips bark beetle. The photochemical [2 + 2] cyclization of Ipsdienol was also studied.

  苯基二甲基硅基铜与 1,2-丙二烯反应，然后在 Pd0 催化下将生成的铜中间体与烯烃卤化物偶联，就能以高产率生成含烯丙硅烷的二烯。与乙烯基溴偶联可得到 2-苯基二甲基硅甲基丁-1,3-二烯，它是合成(±)-Ipsenol 和(±)-Ipsdienol 的异戊烯基结构单元，而 (±)-Ipsenol 和 (±)-Ipsdienol 是 Ips 树皮甲虫的聚集信息素。此外，还研究了 Ipsdienol 的光化学 [2 + 2] 环化过程。
• Noncascade Tandem Transformations Involving Allylic Silanes. 1. Pericyclic and Ionic Reactions Combined into “One-Pot” Sequences
  作者：Michael G. Organ、Derick D. Winkle

  DOI：10.1021/jo962025f

  日期：1997.3.1