1-tosyl-7-(trimethylsilyl)-(E,Z)-5-heptene | 136066-77-8

• 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: 1-tosyl-7-(trimethylsilyl)-(E,Z)-5-heptene
• CAS: 136066-77-8；136066-78-9
• 化学式: C₁₇H₂₈O₃SSi
• 分子量: 340.559
• InChiKey: KYFUPVYDBWDPIR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  22.0
• 可旋转键数：
  9.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-tosyl-7-(trimethylsilyl)-(E,Z)-5-heptene 在 正丁基锂 、 二异丁基氢化铝 作用下， 以 正己烷 、 二甲基亚砜 、 苯 为溶剂， 反应 98.0h， 生成 1-methoxy-9-(trimethylsilyl)-(E,Z)-1,7-nonadiene
  参考文献：
  名称：

  Intramolecular anodic olefin coupling reactions: a useful method for carbon-carbon bond formation

  摘要：

  The utility of intramolecular anodic olefin coupling reactions for effecting carbon-carbon bond formation has been examined. All of the successful cyclizations studied utilized either an alkyl or silyl enol ether as one of the participating olefins. The enol ethers could be coupled to simple alkyl olefins, styrenes, and allylsilanes in isolated yields ranging from 57 to 84%. The reactions were found to be effective for generating both five- and six-membered rings. The best conditions for cyclization utilized a reticulated vitreous carbon anode, constant-current conditions in an undivided cell, and a lithium perchlorate in either 50% methanol/tetrahydrofuran or 20% methanol/dichloromethane electrolyte solution. The use of an allylsilane as one of the participating olefins allowed for the regiospecific formation of olefinic products. In addition to the olefinic products, these reactions produced a small amount of a cyclized ether product in which the silyl group had not been eliminated. Deuterium-labeling studies showed that at least half of this ether byproduct arose from intramolecular migration of the methoxy group that was initially part of the starting enol ether to the carbon-beta to the silyl group. Intramolecular migration reactions of this type were found to participate in a number of the reported cyclization reactions.

  DOI：

  10.1021/ja00019a038
• 作为产物：
  描述：

  (2-trimethylsilylethylidene)triphenylphosphorane 在 正丁基锂 作用下， 反应 18.67h， 生成 1-tosyl-7-(trimethylsilyl)-(E,Z)-5-heptene
  参考文献：
  名称：

  Intramolecular anodic olefin coupling reactions: a useful method for carbon-carbon bond formation

  摘要：

  The utility of intramolecular anodic olefin coupling reactions for effecting carbon-carbon bond formation has been examined. All of the successful cyclizations studied utilized either an alkyl or silyl enol ether as one of the participating olefins. The enol ethers could be coupled to simple alkyl olefins, styrenes, and allylsilanes in isolated yields ranging from 57 to 84%. The reactions were found to be effective for generating both five- and six-membered rings. The best conditions for cyclization utilized a reticulated vitreous carbon anode, constant-current conditions in an undivided cell, and a lithium perchlorate in either 50% methanol/tetrahydrofuran or 20% methanol/dichloromethane electrolyte solution. The use of an allylsilane as one of the participating olefins allowed for the regiospecific formation of olefinic products. In addition to the olefinic products, these reactions produced a small amount of a cyclized ether product in which the silyl group had not been eliminated. Deuterium-labeling studies showed that at least half of this ether byproduct arose from intramolecular migration of the methoxy group that was initially part of the starting enol ether to the carbon-beta to the silyl group. Intramolecular migration reactions of this type were found to participate in a number of the reported cyclization reactions.

  DOI：

  10.1021/ja00019a038

文献信息

• β-Silicon Effect Enables Metal-Free Site-Selective Intermolecular Allylic C–H Amination
  作者：Shuang Lin、Yuan Liu、Kun-Yu Gao、Zhi-Hao Chen、Jiasheng Qian、Xiao-Bin Liu、Qingjiang Li、Honggen Wang

  DOI：10.1021/acscatal.4c02393

  日期：2024.6.7

  derivatives play pivotal roles across diverse applications, yet their current synthetic methods often entail intricate functional group manipulations. Despite the widespread use of allyl silanes as carbon nucleophiles in organic synthesis, their participation in allylic C–H functionalization has been underexplored. Herein, we unveil a metal-free intermolecular C–H amination of allyl silanes facilitated

  α-氨基硅烷及其衍生物在多种应用中发挥着关键作用，但其当前的合成方法通常需要复杂的官能团操作。尽管烯丙基硅烷在有机合成中广泛用作碳亲核试剂，但它们在烯丙基 C-H 官能化中的作用尚未得到充分研究。在此，我们揭示了β-硅效应促进的烯丙基硅烷的无金属分子间C-H胺化。该方案产生具有优异位点选择性的 α-氨基硅烷。值得注意的是，由于温和的反应条件和反应途径，无需脱甲硅烷基即可高产率合成各种仲和叔 α-氨基硅烷。机理阐明强调了甲硅烷基部分对烯烃的活化作用，以及其对相邻发展正电荷的稳定影响，选择性地驱动闭合过渡态，确保位点选择性。