(E)-1-(phenylseleno)-2-(triisopropylsilyl)ethene | 155623-71-5

• 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: (E)-1-(phenylseleno)-2-(triisopropylsilyl)ethene
• 英文别名: [(E)-2-phenylselanylethenyl]-tri(propan-2-yl)silane
• CAS: 155623-71-5
• 化学式: C₁₇H₂₈SeSi
• 分子量: 339.455
• InChiKey: RSGRHGBGOAAXPZ-OUKQBFOZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  di-tert-butyl methylenemalonate 、 (E)-1-(phenylseleno)-2-(triisopropylsilyl)ethene 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以59%的产率得到di-tert-butyl 2-<(phenylseleno)-3-(triisopropylsilyl)>cyclobutane-1,1-dicarboxylate
  参考文献：
  名称：

  [2 + 1] and [2 + 2] Cycloaddition Reaction of 1-Seleno-2-silylethenes to Methylenemalonate Esters: A Novel Ring Contraction of Cyclobutane to Cyclopropane

  摘要：

  Reaction of (E)-1-(phenylseleno)-2-silylethenes 1a-c and methylenemalonate esters 2a,b with Lewis acids (TiCl4-1/2Ti((OPr)-Pr-i)(4), BF3 . Et(2)O, SnCl2 and ZnBr2) gave [2 + 2] cycloadducts in addition to [2 + 1] cycloadducts. This is a novel mode of reactivity for 1-seleno-2-silylethenes. [2 + 1] and [2 + 2] cycloaddition can be controlled by Lewis acids, the substituents on silicon, temperature, and time. A novel rearrangement of cyclobutane to cyclopropane in the presence of ZnBr2 under reversible conditions was also discovered. The stereochemistry of the cyclopropane products was elucidated by NMR.

  DOI：

  10.1021/jo00125a046
• 作为产物：
  描述：

  (E)-1-(triisopropylsilyl)-2-(tributylstannyl)ethene 、 二苯基二硒醚 在 正丁基锂 作用下， 生成 (E)-1-(phenylseleno)-2-(triisopropylsilyl)ethene
  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

• A Novel Strategy for Cyclobutane Formation. Fine Tuning of Cyclobutanation vs Cyclopropanation
  作者：Shoko Yamazaki、Hitoshi Kumagai、Shinichi Yamabe、Kagetoshi Yamamoto

  DOI：10.1021/jo972310e

  日期：1998.5.1

  The reactions of (E)-1-(phenyl seleno)-2-(trimethylsilyl)ethene (la) and (E)-1-(phenylseleno)-2-(triethylsilyl)ethene (1b) with dimethyl 1,1-dicyanoethene-2,2-dicarboxylate (2) in the presence of SnCl4 in CH2Cl2 at -78 degrees C for 1 h exclusively afforded [2 + 2] cycloadducts 3a and 3b in 71% and 78% yields, respectively. The exclusive [2 + 2] selectivity in the reaction of 1 with 2 in the presence of SnCl4 is explained by destabilization of the proposed selenium-bridged intermediate that would lead to the [2 + 1] adduct by the presence of the two electron-withdrawing cyano groups. The reaction of la with 2 at 0 degrees C to room temperature in the presence of ZnBr2 gave a regioisomeric [2 + 2] cycloadduct 7a in low yield along with a corresponding desilylated cyclobutane 8 as the major product in moderate to good yield. The origin of the Lewis acid dependence of the regioselectivity was deduced from a theoretical comparison of stability of Lewis acid complexes.
• 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.
• [2 + 1] and [2 + 2] Cycloaddition Reaction of 1-Seleno-2-silylethenes to Methylenemalonate Esters: A Novel Ring Contraction of Cyclobutane to Cyclopropane
  作者：Shoko Yamazaki、Mayumi Tanaka、Takashi Inoue、Naokazu Morimoto、Hitoshi Kumagai、Kagetoshi Yamamoto

  DOI：10.1021/jo00125a046

  日期：1995.10

  Reaction of (E)-1-(phenylseleno)-2-silylethenes 1a-c and methylenemalonate esters 2a,b with Lewis acids (TiCl4-1/2Ti((OPr)-Pr-i)(4), BF3 . Et(2)O, SnCl2 and ZnBr2) gave [2 + 2] cycloadducts in addition to [2 + 1] cycloadducts. This is a novel mode of reactivity for 1-seleno-2-silylethenes. [2 + 1] and [2 + 2] cycloaddition can be controlled by Lewis acids, the substituents on silicon, temperature, and time. A novel rearrangement of cyclobutane to cyclopropane in the presence of ZnBr2 under reversible conditions was also discovered. The stereochemistry of the cyclopropane products was elucidated by NMR.