((1-(4-methoxyphenyl)-2-phenylvinyl)oxy)trimethylsilane | 71597-81-4

• 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-(4-methoxyphenyl)-2-phenylvinyl)oxy)trimethylsilane
• 英文别名: {[1-(4-Methoxyphenyl)-2-phenylethenyl]oxy}(trimethyl)silane；[1-(4-methoxyphenyl)-2-phenylethenoxy]-trimethylsilane
• CAS: 71597-81-4
• 化学式: C₁₈H₂₂O₂Si
• 分子量: 298.457
• InChiKey: MJUNACGOOQYOIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.04
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ((1-(4-methoxyphenyl)-2-phenylvinyl)oxy)trimethylsilane 在 甲基锂 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 0.17h， 生成
  参考文献：
  名称：

  由烯醇化锂的1,3-金属酸酯重排引发的酮烯醇酸酯的立体选择性合成三取代乙烯基硼酸酯。

  摘要：

  据报道，通过在无过渡金属的条件下直接酮化锂酮烯醇盐进行三取代乙烯基硼酸酯的空前的立体选择性合成。烯醇酸锂的立体有择CO硼化反应是通过C结合的硼烯醇盐由羰基诱导的1,3-金属盐重排触发的。DFT计算和控制实验表明，立体选择性受空间位阻的控制。使用新开发的方法可以方便地合成各种立体有择的三取代乙烯基硼酸酯，以及几种四取代乙烯基硼酸酯。基于立体定向乙烯基硼酸酯的转化，有效地获得了烯雌酚的单一异构体。

  DOI：

  10.1002/anie.201909235
• 作为产物：
  描述：

  S-α-trimethylsilylbenzyl 4-methoxythiobenzoate 以 氘代苯 为溶剂， 反应 8.0h， 以91%的产率得到((1-(4-methoxyphenyl)-2-phenylvinyl)oxy)trimethylsilane
  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

• Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/N,N′-Aromatic Bidentate Base Systems. IV. Bismuth(III) Halide/N,N′-Bidentate Ligand (1 : 1) Systems
  作者：Brian R. Davis、Mark G. Hinds

  DOI：10.1071/c96107

  日期：——

  The generation of a number of 1,2-diarylcyclopropane-1,2-diols is reported. Reaction of these in situ with acid gives, primarily, an α,β-unsaturated ketone in which the aryl substituent attached to the double bond is that which is best able to stabilize a benzylic cation. It is proposed that the reaction proceeds by O-protonation of the cyclopropane-1,2-diol, followed by loss of water and opening of the resulting cyclopropyl cation and final deprotonation. Such initial O-protonation contrasts with the C-protonation normally observed in the acidolysis of cyclopropanols and other dialkyl- and alkylaryl-cyclopropane-1,2-diols.

  报道了一系列1,2-二芳基环丙烷-1,2-二醇的生成。这些物质与酸在原位反应主要生成一种α,β-不饱和酮，其中连接到双键的芳基取代基是最能稳定苄基阳离子的。据推测，该反应通过环丙烷-1,2-二醇的O-质子化开始，随后失去水分并打开所得环丙基阳离子，最终去质子化。这种初始的O-质子化与通常观察到的C-质子化形成鲜明对比，后者在环丙醇和其他二烷基和烷基芳基环丙烷-1,2-二醇的酸解中通常被观察到。
• 一种烯基硼化合物及其制备方法与应用
  申请人：中国科学院兰州化学物理研究所

  公开号：CN112010881B

  公开（公告）日：2021-09-03

  本发明公开了一种烯基硼化合物及其制备方法与应用。所述制备方法包括：在保护性气氛中，使包含有烯醇锂试剂、双硼试剂、添加剂和溶剂的均匀混合反应体系于25℃～160℃反应1～24h，再经后处理制得烯基硼化合物。本发明提供的烯基硼化合物的制备方法以简单、经济、易得的原料为底物，在不需要金属催化剂的参与下高效的、高选择性合成烯基硼化合物，反应条件相对温和、操作简单、原料经济易得、反应高效，且具有良好的官能团兼容性，“一锅法”实现了烯基硼化合物的合成，避免了金属过度残留的问题，获得的烯基硼化合物在医药合成中间体以及有机光电材料科学中有很大的应用前景。
• 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.
• Stereoselective Synthesis of Trisubstituted Vinylboronates from Ketone Enolates Triggered by 1,3‐Metalate Rearrangement of Lithium Enolates
  作者：Yue Hu、Wei Sun、Tao Zhang、Nuo Xu、Jianeng Xu、Yu Lan、Chao Liu

  DOI：10.1002/anie.201909235

  日期：2019.10.28

  unprecedented stereoselective synthesis of trisubstituted vinylboronates is reported to proceed by direct borylation of lithium ketone enolates under transition-metal-free conditions. The stereospecific C-O borylation of lithium enolates was triggered by a carbonyl-induced 1,3-metalate rearrangement via a C-bound boron enolate. DFT calculations and control experiments revealed that the stereoselectivity is controlled

  据报道，通过在无过渡金属的条件下直接酮化锂酮烯醇盐进行三取代乙烯基硼酸酯的空前的立体选择性合成。烯醇酸锂的立体有择CO硼化反应是通过C结合的硼烯醇盐由羰基诱导的1,3-金属盐重排触发的。DFT计算和控制实验表明，立体选择性受空间位阻的控制。使用新开发的方法可以方便地合成各种立体有择的三取代乙烯基硼酸酯，以及几种四取代乙烯基硼酸酯。基于立体定向乙烯基硼酸酯的转化，有效地获得了烯雌酚的单一异构体。