3-(3-(dichloroacetoxy)oct-1-enyl)trimethylsilane | 1246289-30-4

• 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
• 英文名称: 3-(3-(dichloroacetoxy)oct-1-enyl)trimethylsilane
• 英文别名: 3-Trimethylsilyloct-1-en-3-yl 2,2-dichloroacetate；3-trimethylsilyloct-1-en-3-yl 2,2-dichloroacetate
• CAS: 1246289-30-4
• 化学式: C₁₃H₂₄Cl₂O₂Si
• 分子量: 311.324
• InChiKey: GEGRTESLIRZMDA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.72
• 重原子数：
  18
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 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：

  3-(3-(dichloroacetoxy)oct-1-enyl)trimethylsilane 以 萘 、 氘代苯 为溶剂， 反应 0.33h， 以19%的产率得到trimethylsilyl-3 octadiene-1,3
  参考文献：
  名称：

  Thermal [3,3]-rearrangement of 1,1-disubstituted allyl carboxylates: lone pair participation and the geminal bond participation

  摘要：

  The diastereoselectivity of the [3,3]-rearrangement of 1,1-disubsstituted ally! carboxylates was studied. In this heteroatom-containing system, the transition state has a boat-like transition structure (TS) because of the participation of the lone pairs and the secondary orbital interaction. Although the TS for the [1,3]-rearrangement has a far higher barrier, it does not proceed in the usual antarafacial manner due to the cyclic orbital interaction among two lone pairs of the carboxylate and the allylic lumo. In conjunction with the geminal bond participation, delocalization to the sigma-bond at the Z-position shows a bonding character in the transition state of the [3,3]-rearrangement. Therefore, we predicted that a more electron-withdrawing sigma-bond prefers the Z-position in the product. We designed the 1,1-disubstituted substrates with trimethylsilyl and pentyl groups, and found that the trimethylsilyl group prefers the Z-position despite its steric bulkiness. We confirmed our prediction by experimentation. This Z-selectivity was improved when a trimethylgermyl group was used. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.06.016
• 作为产物：
  描述：

  二氯乙酰氯 、 3-(3-hydroxy-1-octenyl)trimethylsilane 在 乙基氯化镁 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以31%的产率得到3-(3-(dichloroacetoxy)oct-1-enyl)trimethylsilane
  参考文献：
  名称：

  Thermal [3,3]-rearrangement of 1,1-disubstituted allyl carboxylates: lone pair participation and the geminal bond participation

  摘要：

  The diastereoselectivity of the [3,3]-rearrangement of 1,1-disubsstituted ally! carboxylates was studied. In this heteroatom-containing system, the transition state has a boat-like transition structure (TS) because of the participation of the lone pairs and the secondary orbital interaction. Although the TS for the [1,3]-rearrangement has a far higher barrier, it does not proceed in the usual antarafacial manner due to the cyclic orbital interaction among two lone pairs of the carboxylate and the allylic lumo. In conjunction with the geminal bond participation, delocalization to the sigma-bond at the Z-position shows a bonding character in the transition state of the [3,3]-rearrangement. Therefore, we predicted that a more electron-withdrawing sigma-bond prefers the Z-position in the product. We designed the 1,1-disubstituted substrates with trimethylsilyl and pentyl groups, and found that the trimethylsilyl group prefers the Z-position despite its steric bulkiness. We confirmed our prediction by experimentation. This Z-selectivity was improved when a trimethylgermyl group was used. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.06.016

文献信息

• Thermal [3,3]-rearrangement of 1,1-disubstituted allyl carboxylates: lone pair participation and the geminal bond participation
  作者：Yuji Naruse、Aya Deki、Katsura Yamada

  DOI：10.1016/j.tet.2010.06.016

  日期：2010.8

  The diastereoselectivity of the [3,3]-rearrangement of 1,1-disubsstituted ally! carboxylates was studied. In this heteroatom-containing system, the transition state has a boat-like transition structure (TS) because of the participation of the lone pairs and the secondary orbital interaction. Although the TS for the [1,3]-rearrangement has a far higher barrier, it does not proceed in the usual antarafacial manner due to the cyclic orbital interaction among two lone pairs of the carboxylate and the allylic lumo. In conjunction with the geminal bond participation, delocalization to the sigma-bond at the Z-position shows a bonding character in the transition state of the [3,3]-rearrangement. Therefore, we predicted that a more electron-withdrawing sigma-bond prefers the Z-position in the product. We designed the 1,1-disubstituted substrates with trimethylsilyl and pentyl groups, and found that the trimethylsilyl group prefers the Z-position despite its steric bulkiness. We confirmed our prediction by experimentation. This Z-selectivity was improved when a trimethylgermyl group was used. (C) 2010 Elsevier Ltd. All rights reserved.