S-α,α-bis(trimethylsilyl)methyl (E)-thiocinnamate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: S-α,α-bis(trimethylsilyl)methyl (E)-thiocinnamate
• 英文别名: S-[bis(trimethylsilyl)methyl] (E)-3-phenylprop-2-enethioate
• 化学式: C₁₆H₂₆OSSi₂
• 分子量: 322.619
• InChiKey: ZLMSYQBOFHNYAV-OUKQBFOZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.08
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 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,α-bis(trimethylsilyl)methyl (E)-thiocinnamate 以 氘代苯 为溶剂， 反应 26.0h， 生成 (1Z,3E)-1-trimethylsilylthio-2-trimethylsiloxy-4-phenyl-1,3-butadiene 、 (1E,3E)-1-trimethylsilylthio-2-trimethylsiloxy-4-phenyl-1,3-butadiene
  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：

  肉桂酸 、 bis(trimethylsilyl)methanethiol 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68%的产率得到S-α,α-bis(trimethylsilyl)methyl (E)-thiocinnamate
  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

• 1,4-Silatropy of <i>S</i>-α-Silylbenzyl Thioesters:  A Convenient Route to Silyl Enol and Dienol Ethers Accompanied by C−C Bond Formation via Thiocarbonyl Ylides
  作者：Jinil Choi、Eiichiro Imai、Masatoshi Mihara、Yoji Oderaotoshi、Satoshi Minakata、Mitsuo Komatsu

  DOI：10.1021/jo026211z

  日期：2003.8.1

  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.