1-(phenylseleno)-2-(trimethylsilyl)ethene | 130267-88-8

• 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-(trimethylsilyl)ethene
• 英文别名: (E)-1-(phenylseleno)-2-(trimethylsilyl)ethene；(e)-2-Trimethylsilyl-1-phenylselenoethene；trimethyl-[(E)-2-phenylselanylethenyl]silane
• CAS: 130267-88-8
• 化学式: C₁₁H₁₆SeSi
• 分子量: 255.294
• InChiKey: FKHOLHHPSQIKEE-MDZDMXLPSA-N

物化性质

• 沸点：
  80-82 °C(Press: 1 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  2.41
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 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-(trimethylsilyl)ethene 在 锂硼氢 、 三乙基硼氢化锂 、 三乙胺 、 zinc dibromide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 74.25h， 生成 tert-butyl 3,3-dimethyl-2-[(phenylseleno)(trimethylsilyl)methyl]-1,2-cis-cyclopropanecarboxylate
  参考文献：
  名称：

  Lewis Acid促进了1-Seleno-2-silylethene与三羰基取代的烯烃的[2 +1]环加成反应。

  摘要：

  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。

  DOI：

  10.1021/jo9622486
• 作为产物：
  描述：

  三甲基乙炔基硅 在 正丁基锂 作用下， 生成 1-(phenylseleno)-2-(trimethylsilyl)ethene
  参考文献：
  名称：

  Cyclopentenone annulation reaction using (E)-1-(phenylseleno)-2-(trimethylsilyl)ethene

  摘要：

  DOI：

  10.1016/0040-4039(90)80184-n

文献信息

• Lewis Acid-Promoted [2 + 1] Cycloaddition Reactions of a 1-Seleno-2-silylethene to 2-Phosphonoacrylates:  Stereoselective Synthesis of a Novel Functionalized α-Aminocyclopropanephosphonic Acid
  作者：Shoko Yamazaki、Takashi Takada、Tomomi Imanishi、Yumiko Moriguchi、Shinichi Yamabe

  DOI：10.1021/jo9805450

  日期：1998.8.1

  Stereoselective SnCl(4)-promoted [2 + 1] cycloaddition reactions of 1-seleno-2-silylethene 1 with 2-phosphonoacrylates 2 lead to highly functionalized cyclopropanephosphonate esters 3 in high yields. The cyclopropane products 3 are potentially versatile starting materials for biologically important compounds. Stereoselective synthesis of a novel functionalized alpha-aminophosphonic acid derivative

  1-硒基-2-甲硅烷基乙烯1与2-膦酰基丙烯酸酯2的立体选择性SnCl（4）促进[2 +1]环加成反应以高收率产生高度官能化的环丙烷膦酸酯3。环丙烷产物3是生物上重要的化合物的潜在通用原料。从环加合物3b实现了立体选择性合成新型的官能化的α-氨基膦酸衍生物，其为（Z）-2，3-甲氨基高丝氨酸13的类似物。通过考虑2-SnCl（4）复杂的结构解释了[2 +1]环加成中的立体选择性。
• Synthesis of novel all-cis-functionalized cyclopropane template-assembled collagen models†
  作者：Shoko Yamazaki、Mari Sakamoto、Michiko Suzuri、Masamitsu Doi、Takashi Nakazawa、Yuji Kobayashi

  DOI：10.1039/b103887g

  日期：——

  An all-cis-functionalized cyclopropane template to connect the three peptide chains in a collagen model is designed. Stereoselective synthesis of cyclopropane-assembled collagen-model 2b with the minimum unit of Gly-Pro-Pro is based on a novel 1-seleno-2-silylethene [2 + 1] cycloaddition strategy. Reaction of the 1-seleno-2-silylethene 4 with triester-substituted olefin 5 in the presence of ZnI2 gives [2 + 1] cycloadduct 6 stereoselectively. Cyclopropane 6 is selectively transformed into triol 10 in four steps. The reaction of 10 and three equivalents of N-Boc-Pro-Pro-Gly-OH in the presence of WSC–DMAP and subsequent deprotection with TFA gives 2b.

  设计了一种全顺式功能化的环丙烷模板，用于连接胶原模型中的三条肽链。基于一种新颖的1-硒-2-硅乙烯[2 + 1]环加成策略，立体选择性合成了具有最小单元Gly-Pro-Pro的环丙烷组装胶原模型2b。1-硒-2-硅乙烯4与三酯取代的烯烃5在ZnI2存在下反应，选择性生成[2 + 1]环加成产物6。环丙烷6经过四个步骤选择性转化为三醇10。10与三当量N-Boc-Pro-Pro-Gly-OH在WSC–DMAP的存在下反应，随后用TFA去保护，得到2b。
• Highly Efficient [2+1] Cycloaddition Reactions of a 1-Seleno-2-silylethene to 2-Phosphonoacrylates: Synthesis of Novel Functionalized Cyclopropanephosphonic Acid Esters
  作者：Shoko Yamazaki、Tomomi Imanishi、Yumiko Moriguchi、Takashi Takada

  DOI：10.1016/s0040-4039(97)01436-6

  日期：1997.9

  1-Seleno-2-silylethene 1 undergoes stereoselective SnCl4-promoted [2+1] cycloaddition reactions with 2-phosphonoacrylates 2 in high yields; the resulting highly functionalized cyclopropanephosphonic acid ester products 3 are versatile starting materials for biologically important compounds. © 1997 Elsevier Science Ltd.

  1-硒-2- silylethene 1所经历立体选择性的SnCl 4促进的[2 + 1]与2- phosphonoacrylates环加成反应2以高产率; 所得的高度官能化的环丙烷膦酸酯产物3是生物上重要的化合物的通用原料。©1997爱思唯尔科学有限公司。
• [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.
• 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.