ethyl (E)-2-deuterio-2-(dimethylphenylsilyl)-4-phenylbut-3-enoate | 187950-80-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl (E)-2-deuterio-2-(dimethylphenylsilyl)-4-phenylbut-3-enoate
• 英文别名: ethyl (E)-2-deuterio-2-[dimethyl(phenyl)silyl]-4-phenylbut-3-enoate
• CAS: 187950-80-7
• 化学式: C₂₀H₂₄O₂Si
• 分子量: 325.487
• InChiKey: ZZMXNNPITZZARS-VYCFBMKRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.25
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  ethyl (E)-2-deuterio-2-(dimethylphenylsilyl)-4-phenylbut-3-enoate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 0.5h， 生成 (E)-2-deuterio-2-[dimethyl(phenyl)silyl]-4-phenylbut-3-en-1-ol
  参考文献：
  名称：

  A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds

  摘要：

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.

  DOI：

  10.1021/jo961952j
• 作为产物：
  描述：

  反-苯乙烯乙酸 在 dirhodium tetraacetate 、 ABSA 、 硫酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 3.83h， 生成 ethyl (E)-2-deuterio-2-(dimethylphenylsilyl)-4-phenylbut-3-enoate
  参考文献：
  名称：

  A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds

  摘要：

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.

  DOI：

  10.1021/jo961952j

文献信息

• Mechanism of metal-carbenoid insertion into the SiH bond
  作者：Yannick Landais、Liliana Parra-Rapado、Denis Planchenault、Valéry Weber

  DOI：10.1016/s0040-4039(96)02285-x

  日期：1997.1

  Kinetic investigations on the insertion of metal-carbenoid intermediates into the SI-H bond have been carried out. A kinetic isotope effect of 1.5 was found and the plot of log k(X)/k(H) vs sigma for the reaction of arylsilanes with EDA, gave a straight line with rho = -0.31. It was thus concluded that the insertion proceeds through a concerted pathway with development of a small positive charge at the silicon centre and it relatively early transition state. Copyright (C) 1996 Elsevier Science Ltd