S-α-trimethylsilylbenzyl (E)-thiocrotonate | 403520-38-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: S-α-trimethylsilylbenzyl (E)-thiocrotonate
• 英文别名: S-[phenyl(trimethylsilyl)methyl] (E)-but-2-enethioate
• CAS: 403520-38-7
• 化学式: C₁₄H₂₀OSSi
• 分子量: 264.464
• InChiKey: IBEQMQZKDFXGOZ-WEVVVXLNSA-N

物化性质

• 沸点：
  336.9±31.0 °C(Predicted)
• 密度：
  1.007±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.44
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  S-α-trimethylsilylbenzyl (E)-thiocrotonate 以 氘代苯 为溶剂， 反应 24.0h， 以14%的产率得到2-phenyl-3-trimethylsiloxy-5-methylthiophene
  参考文献：
  名称：

  1,4-Silatropy of S-α-Silylbenzyl Thioesters:  A Convenient Route to Silyl Enol and Dienol Ethers Accompanied by C−C Bond Formation via Thiocarbonyl Ylides

  摘要：

  A novel convenient method for the generation of thiocarbonyl ylides from readily accessible starting materials and the first synthetic application of in situ generated ylides in the synthesis of silyl enol and dienol ethers, accompanied by C-C bond formation, is described. Under completely neutral conditions without any catalyst or additive, thermal reactions of S-alpha-silylbenzyl thioesters in sealed tubes at 180 degreesC provided silyl enol and dienol ethers in good to excellent yields with high stereoselectivities. This procedure consists of a multistep reaction in a one-pot process, i.e., 1,4-silatropy of S-alpha-silylbenzyl thioesters to give thiocarbonyl ylides, 1,3-electrocyclization of the ylides to give thiiranes, and the extrusion of sulfur from thiiranes to give silyl enol and dienol ethers.

  DOI：

  10.1021/jo026211z
• 作为产物：
  描述：

  巴豆酸 、 α-(trimethylsilyl)benzylthiol 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以78%的产率得到S-α-trimethylsilylbenzyl (E)-thiocrotonate
  参考文献：
  名称：

  1,4-Silatropy of S-α-Silylbenzyl Thioesters:  A Convenient Route to Silyl Enol and Dienol Ethers Accompanied by C−C Bond Formation via Thiocarbonyl Ylides

  摘要：

  A novel convenient method for the generation of thiocarbonyl ylides from readily accessible starting materials and the first synthetic application of in situ generated ylides in the synthesis of silyl enol and dienol ethers, accompanied by C-C bond formation, is described. Under completely neutral conditions without any catalyst or additive, thermal reactions of S-alpha-silylbenzyl thioesters in sealed tubes at 180 degreesC provided silyl enol and dienol ethers in good to excellent yields with high stereoselectivities. This procedure consists of a multistep reaction in a one-pot process, i.e., 1,4-silatropy of S-alpha-silylbenzyl thioesters to give thiocarbonyl ylides, 1,3-electrocyclization of the ylides to give thiiranes, and the extrusion of sulfur from thiiranes to give silyl enol and dienol ethers.

  DOI：

  10.1021/jo026211z

文献信息

• A novel synthesis of silyl enol ethers from α-silylbenzylthiols and carboxylic acid derivatives via CC bond formation; thermal rearrangement of S-α-silylbenzyl thioesters
  作者：Mitsuo Komatsu、Choi Jinil、Eiichiro Imai、Yoji Oderaotoshi、Satoshi Minakata

  DOI：10.1016/s0040-4039(01)02029-9

  日期：2001.12

  A new procedure for the synthesis of silyl enol ethers from S-α-silylbenzyl thioesters without need for either bases or catalysts via CC bond formation is described. Solutions of S-α-silylbenzyl thioesters were simply heated at 180°C for 24 h in a sealed tube to give silyl enol ethers in good yields with high stereoselectivity. Cyclization of the dipoles generated by thermal rearrangement of the silyl

  描述了由S -α-甲硅烷基苄基硫代酯合成甲硅烷基烯醇醚的新方法，该过程不需要通过C viaC键形成的碱或催化剂。解小号-α-silylbenzyl硫酯是在一个密封管中在180℃下简单地加热24小时，得到甲硅烷基烯醇醚以良好的收率高立体选择性。通过甲硅烷基基团的热重排和消除硫产生的偶极的环化提供了甲硅烷基烯醇醚。