methyl (E)-2,3-bis(phenylseleno)acrylate | 114221-64-6

• 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: methyl (E)-2,3-bis(phenylseleno)acrylate
• 英文别名: methyl (E)-2,3-bis(phenylselen)propenoate；methyl (E)-2,3-bis(phenylselanyl)acrylate；methyl (2E)-2,3-bis(phenylseleno)acrylate；methyl (E)-2,3-bis(phenylselanyl)prop-2-enoate
• CAS: 114221-64-6
• 化学式: C₁₆H₁₄O₂Se₂
• 分子量: 396.206
• InChiKey: NSERJOUPJHWWIG-NTCAYCPXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.06
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  二苯基二硒醚 、 丙炔酸甲酯 在 [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]gold bis(trifluoromethanesulfonyl)imidate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以94%的产率得到methyl (E)-2,3-bis(phenylseleno)acrylate
  参考文献：
  名称：

  使用硒阳离子作为温和氧化剂的金氧化还原催化。

  摘要：

  开发了金催化的炔烃和丙二烯二硒化反应。各种底物均实现了优异的区域选择性（反式）和良好至优异的收率（2% 催化剂负载量时收率高达 98%）。机理研究揭示了乙烯基金（I）中间体的形成，随后分子间硒阳离子迁移，表明金（I/III）氧化还原过程在温和条件下成功实施。

  DOI：

  10.1002/chem.202000166

文献信息

• Chemoselective and metal-free reduction of α,β-unsaturated ketones by <i>in situ</i> produced benzeneselenol from <i>O</i>-(<i>tert</i>-butyl) Se-phenyl selenocarbonate
  作者：Andrea Temperini、Marco Ballarotto、Carlo Siciliano

  DOI：10.1039/d0ra07128e

  日期：——

  The carbon–carbon double bond of arylidene acetones and chalcones can be selectively reduced with benzeneselenol generated in situ by reacting O-(tert-butyl) Se-phenyl selenocarbonate with hydrochloric acid in ethanol. This mild, metal-free and experimentally simple reduction procedure displays considerable functional-group compatibility, products are obtained in good to excellent yields, and the use

  亚芳基丙酮和查耳酮的碳碳双键可以通过O- (叔丁基)硒苯基硒代碳酸酯与盐酸在乙醇中的反应原位产生的苯硒醇选择性还原。这种温和、无金属且实验简单的还原过程显示出相当大的官能团兼容性，产品的收率非常好，并且避免使用有毒的 Se/CO 混合物和 NaSeH，或有气味且对空气敏感的苯硒醇.
• Cesium Salt-Catalyzed Addition of Diphenyl Dichalcogenides to Alkynes: Selective Synthesis of Bis- and Mono(phenylchalcogeno)alkenes
  作者：Yutaka Nishiyama、Haruko Ohnishi、Yuya Koguma

  DOI：10.1246/bcsj.82.1170

  日期：2009.9.15

  A cesium salt has a unique catalytic ability for the reaction of alkynes with diphenyl dichalcogenides. When the diphenyl dichalcogenides, such as the disulfide, diselenide, or ditelluride, were allowed to react with alkynes in the presence of a catalytic amount of a cesium fluoride or carbonate, the bisphenylchalcogenolation of the alkynes efficiently proceeded to give the corresponding vic-bis(phenylchalcogeno)alkenes in moderate to good yields with high selectivity. When H2O was added to the reaction medium, monophenylchalcogenolation of the alkynes occurred giving the mono(phenylchalcogeno)alkenes in moderate yields.

  铯盐对炔烃与二苯基二硫属化物的反应具有独特的催化能力。当二苯基二硫属化物，例如二硫化物、二硒化物或二碲化物，在催化量的氟化铯或碳酸铯存在下与炔烃反应时，炔烃的双苯基硫属元素化反应有效地进行，得到相应的vic-bis(苯基硫属元素）烯烃的产率中等至良好，且选择性高。当将水添加到反应介质中时，发生炔烃的单苯基硫属元素醇化，以中等产率得到单(苯基硫属元素)烯烃。
• ——
  作者：V. P. Ananikov、D. A. Malyshev、I. P. Beletskaya

  DOI：10.1023/a:1022500420741

  日期：——

  Addition of benzeneselenol to terminal alkynes HCdropCR, catalyzed by Pd(0) complexes, leads to formation of mixtures of mono- and bis(phenylseleno)alkenes, depending on the nature of the R substituent. Electron-donor groups (R = Bu, CH2OH, CH2NMe2) give rise to addition according to the Markownikoff rule, whereas from alkynes with electron-acceptor groups (R = Ph, COOMe) mixtures of products are formed as a result of side reactions. A probable reaction mechanism includes oxidative addition of benzeneselenol to the metal, alkyne insertion into the Pd-Se bond, and reductive elimination.
• Free-radical additions of diselenides to dimethyl acetylenedicarboxylate, methyl propiolate, and dimethyl maleate
  作者：Thomas G. Back、M. Vijaya Krishna

  DOI：10.1021/jo00246a023

  日期：1988.5
• Gold Redox Catalysis with a Selenium Cation as a Mild Oxidant
  作者：Jin Wang、Chiyu Wei、Xuming Li、Pengyi Zhao、Chuan Shan、Lukasz Wojtas、Hao Chen、Xiaodong Shi

  DOI：10.1002/chem.202000166

  日期：2020.5.12

  achieved (up to 98 % with 2 % catalyst loading) with a wide range of substrates. Mechanistic investigation revealed the formation of a vinyl gold(I) intermediate followed by an intermolecular selenium cation migration, suggesting that a gold(I/III) redox process was successfully implemented under mild conditions.

  开发了金催化的炔烃和丙二烯二硒化反应。各种底物均实现了优异的区域选择性（反式）和良好至优异的收率（2% 催化剂负载量时收率高达 98%）。机理研究揭示了乙烯基金（I）中间体的形成，随后分子间硒阳离子迁移，表明金（I/III）氧化还原过程在温和条件下成功实施。