1-(phenylseleno)-2-(triethylsilyl)ethene | 155623-70-4

• 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: 1-(phenylseleno)-2-(triethylsilyl)ethene
• 英文别名: (E)-1-(phenylseleno)-2-(triethylsilyl)ethene；triethyl-[(E)-2-phenylselanylethenyl]silane
• CAS: 155623-70-4
• 化学式: C₁₄H₂₂SeSi
• 分子量: 297.374
• InChiKey: UFKZJOAJGKZGEV-OUKQBFOZSA-N

物化性质

• 沸点：
  303.6±34.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.58
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  1-(phenylseleno)-2-(triethylsilyl)ethene 在 lithium aluminium tetrahydride 、 zinc dibromide 作用下， 以 乙醚 为溶剂， 反应 1.0h， 生成 (1R,2S)-1-Formyl-2-((S)-phenylselanyl-triethylsilanyl-methyl)-cyclopropanecarboxylic acid tert-butyl ester
  参考文献：
  名称：

  1-硒代-2-甲硅烷基的[2 +1]环加成反应的利用：2-取代的1-氨基环丙烷-1-羧酸的新型合成。

  摘要：

  DOI：

  10.1021/jo9810821
• 作为产物：
  描述：

  三乙基矽乙炔 、 二苯基二硒醚 在 正丁基锂 、 三正丁基氢锡 作用下， 生成 1-(phenylseleno)-2-(triethylsilyl)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

• Lewis Acid Promoted [2 + 1] Cycloaddition Reactions of 1-Seleno-2-silylethene with Tricarbonyl-Substituted Olefins
  作者：Shoko Yamazaki、Hitoshi Kumagai、Takashi Takada、Shinichi Yamabe、Kagetoshi Yamamoto

  DOI：10.1021/jo9622486

  日期：1997.5.1

  tris(alkoxycarbonyl) olefins 2 or 1,1-bis(alkoxycarbonyl)-2-acyl olefins 3 in the presence of ZnBr(2) at -30 degrees C gave cis-substituted cyclopropanes exclusively. The origin of the cis stereochemistry is ascribed to the synclinal addition path of the ZnBr(2)-coordinated electrophilic olefin to 1. Application of the highly functionalized selenium- and silicon-substituted cyclopropane products to the preparation

  已经研究了在路易斯酸存在下1-硒-2-甲硅烷基1与高度亲电的三羰基取代的烯烃的反应。1-（苯基硒代）-2-（三甲基甲硅烷基）乙烯（1a）与三（烷氧羰基）烯烃2或1,1-双（烷氧羰基）-2-酰基烯烃3在ZnBr（2）存在下于- 30℃仅产生顺式取代的环丙烷。顺式立体化学的起源归因于ZnBr（2）配位的亲电烯烃向1的向向加成路径。高官能化的硒和硅取代的环丙烷产品在制备有用的合成中间体20中的应用还证明了拟除虫菊酯类杀虫剂。
• Chiral Synthesis of Cyclopropanes. Stereoselective [2 + 1] Cycloaddition Reactions of 1-Seleno-2-silylethenes with Di-(−)-menthyl Ethene-1,1-dicarboxylates
  作者：Shoko Yamazaki、Hitomi Kataoka、Shinichi Yamabe

  DOI：10.1021/jo9820925

  日期：1999.4.1

  Reaction of 1-seleno-2-silylethenes 1 with the chiral electrophiles 2, 3, and 4 derived from (-)menthol, in the presence of zinc halides gave the cyclopropane products 5, 6, and 7, respectively, with high diastereoselectivity. The absolute configuration of 5a, prepared by the reaction of 1-(phenylseleno)-2-(trimethylsilyl)ethene (la) and di-(-)-menthyl methylenemalonate (2), was determined to be 2S by conversion to the known chiral compound 11. The proposed mechanism, involving fixation of the (-)-menthyl group to the C=C plane by the Lewis acid in the addition step, is consistent with the experimental observations. A selenium-participating secondary orbital interaction in the synclinal addition path was elucidated by ab initio calculations and explained the observed diasteroselectivity.
• [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.
• 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：——