trans-1-propionyl-2-<(phenylseleno)(trimethylsilyl)methyl>cyclopropane | 137627-85-1

• 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: trans-1-propionyl-2-<(phenylseleno)(trimethylsilyl)methyl>cyclopropane
• 英文别名: trans-1-propionyl-2-(1-(phenylseleno)-1-(trimethylsilyl)methyl)cyclopropane；1-[(1S,2S)-2-[phenylselanyl(trimethylsilyl)methyl]cyclopropyl]propan-1-one
• CAS: 137627-85-1
• 化学式: C₁₆H₂₄OSeSi
• 分子量: 339.411
• InChiKey: LIMNQZIWAUIPQP-ADTLFGHVSA-N

物化性质

• 沸点：
  385.5±38.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  三丁基[(1E)-2-(三甲基硅烷基)乙烯基]锡烷 在 正丁基锂 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 7.0h， 生成 trans-1-propionyl-2-<(phenylseleno)(trimethylsilyl)methyl>cyclopropane
  参考文献：
  名称：

  [2 + 1] Cycloaddition of 1-Seleno-2-silylethenes. Selenium-Assisted 1,2-Silicon Shift for Cyclopropanation

  摘要：

  A novel one-step [2 + 1] cycloaddition synthesis of cyclopropanes has been developed. Reaction of (E)-1-(phenylseleno)-2-silylethenes 1a,b with vinyl ketones 2a-d and acrolein (2e) in the presence of SnCl4 gave cyclopropane products by a formal [2 + 1] cycloaddition accompanied by 1,2-silicon migration rather than by [2 + 2] cycloaddition. This facile 1,2-silicon shift is rationalized by a remarkable selenium effect. A generated beta-silicon-stabilized zwitterion A is transformed by a 1,2-silicon shift to the more stable selenium-bridged intermediate C. Ab initio MO calculations for model compounds clearly demonstrate that the intermediate C is more stable than A. The selenium-bridged geometry of C shows that preference is for formation of a cyclopropane ring instead of a cyclobutane ring.

  DOI：

  10.1021/ja00085a015

文献信息

• [2 + 1] Cycloaddition of (E)-1-(phenylseleno)-2-(trimethylsilyl)ethene. Novel cyclopropane ring formation by a 1,2-shift of a trimethylsilyl group
  作者：Shoko Yamazaki、Shigeki Katoh、Shinichi Yamabe

  DOI：10.1021/jo00027a003

  日期：1992.1

  Reaction of (E)-1-(phenylseleno)-2-(trimethylsilyl)ethene (1) with vinyl ketones 2a-d in the presence of SnCl4 gave cyclopropane products by a formal [2 + 1] cycloaddition accompanied by 1,2-silicon migration rather than [2 + 2] cycloaddition.
• Asymmetric [2 + 1] Cycloaddition Reactions of 1-Seleno-2-silylethene
  作者：Shoko Yamazaki、Mayumi Tanaka、Shinichi Yamabe

  DOI：10.1021/jo960194u

  日期：1996.1.1

  The reaction of (E)-1-(phenylseleno)-2-(trimethylsilyl)ethene (1) and vinyl ketones 2a-d in the presence of a chiral Lewis acid prepared from TiCl4, Ti((OPr)-Pr-i)(4), (R)- or (S)-1,1'-binaphthol (BINOL), and MS4A gave enantiomerically enriched cis cyclopropane products 3a-d. The enantiomeric excess and chemical yield varied depending on the ratio of TiCl4 and Ti((OPr)-Pr-i)(4) to 1. Reproducible results (43-47% ee/33-41% yields) for cis-1-acetyl-2-[(phenylseleno)(trimethylsilyl)methyl]cyclopropane (3a) were obtained using 1.1 equiv of TiCl4, 0.54-0.65 equiv of Ti((OPr)-Pr-i)(4), and 1.65 equiv of BINOL. The observed enantioselectivity was explained by consideration of the structure of the postulated intermediates, alkoxy titanium-carbonyl complexes, via ab initio MO calculations.
• [2 + 1] Cycloaddition of 1-Seleno-2-silylethenes. Selenium-Assisted 1,2-Silicon Shift for Cyclopropanation
  作者：Shoko Yamazaki、Mayumi Tanaka、Akio Yamaguchi、Shinichi Yamabe

  DOI：10.1021/ja00085a015

  日期：1994.3

  A novel one-step [2 + 1] cycloaddition synthesis of cyclopropanes has been developed. Reaction of (E)-1-(phenylseleno)-2-silylethenes 1a,b with vinyl ketones 2a-d and acrolein (2e) in the presence of SnCl4 gave cyclopropane products by a formal [2 + 1] cycloaddition accompanied by 1,2-silicon migration rather than by [2 + 2] cycloaddition. This facile 1,2-silicon shift is rationalized by a remarkable selenium effect. A generated beta-silicon-stabilized zwitterion A is transformed by a 1,2-silicon shift to the more stable selenium-bridged intermediate C. Ab initio MO calculations for model compounds clearly demonstrate that the intermediate C is more stable than A. The selenium-bridged geometry of C shows that preference is for formation of a cyclopropane ring instead of a cyclobutane ring.