trans-1-acetyl-2-(1-(phenylseleno)-1-(triethylsilyl)methyl)cyclopropane

• 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-acetyl-2-(1-(phenylseleno)-1-(triethylsilyl)methyl)cyclopropane
• 英文别名: trans-1-acetyl-2-[1-(phenylseleno)-1-(triethylsilyl)methyl]cyclopropane；1-[(1R,2R)-2-[phenylselanyl(triethylsilyl)methyl]cyclopropyl]ethanone
• 化学式: C₁₈H₂₈OSeSi
• 分子量: 367.465
• InChiKey: WFHYXNINTOSICD-MYFVLZFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.08
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 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：

  三乙基矽乙炔 在 正丁基锂 、 三氯化铝 、 三正丁基氢锡 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 trans-1-acetyl-2-(1-(phenylseleno)-1-(triethylsilyl)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

• Yamazaki Shoko, Tanaka Mayumi, Yamaguchi Akio, Yamabe Shinichi, J. Amer. Chem. Soc, 116 (1994) N 6, S 2356-2365
  作者：Yamazaki Shoko, Tanaka Mayumi, Yamaguchi Akio, Yamabe Shinichi

  DOI：——

  日期：——
• [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.