1-dimethylphenylsilyloxy-1,2-diphenylethene

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1-dimethylphenylsilyloxy-1,2-diphenylethene
• 英文别名: 1,2-diphenylethenoxy-dimethyl-phenylsilane
• 化学式: C₂₂H₂₂OSi
• 分子量: 330.502
• InChiKey: QERLALJHTSBXDX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.31
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  S-α-(dimethyl(phenyl)silyl)benzyl thiobenzoate 以 氘代苯 为溶剂， 反应 5.0h， 以87%的产率得到1-dimethylphenylsilyloxy-1,2-diphenylethene
  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

• Preparation of silyl enol ethers from acyloin derivatives using silyllithium reagents
  作者：Bradley D. Robertson、Aaron M. Hartel

  DOI：10.1016/j.tetlet.2008.01.133

  日期：2008.3

  A new method for the regioselective preparation of silyl enol ethers from acyloin derivatives using silyllithium reagents has been developed. Both dimethylphenyl- and methyldiphenylsilyllithium were found to be effective, the latter providing greater stereocontrol. The reaction is believed to proceed via Brook rearrangement assisted by expulsion of the adjacent leaving group. A number of acyclic acyloin

  已经开发出一种新的方法，用于使用硅烷基锂试剂从酰基糖苷衍生物区域选择性地制备甲硅烷基烯醇醚。发现二甲基苯基-和甲基二苯基甲硅烷基锂都是有效的，后者提供更大的立体控制。据信该反应是通过布鲁克重排而进行的，其中布鲁克被重排，相邻的离去基团被驱逐。使许多无环的酰氯衍生物以良好至优异的产率反应形成相应的甲硅烷基烯醇醚。
• 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.