dimethyl 2,3-bis(phenylselanyl)fumarate | 114221-61-3

• 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: dimethyl 2,3-bis(phenylselanyl)fumarate
• 英文别名: dimethyl (E)-2,3-bis(phenylselanyl)but-2-enedioate
• CAS: 114221-61-3
• 化学式: C₁₈H₁₆O₄Se₂
• 分子量: 454.243
• InChiKey: YJNHQJUVGDNCCV-FOCLMDBBSA-N

物化性质

• 沸点：
  501.4±50.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl 2,3-bis(phenylselanyl)fumarate 在 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 反应 2.5h， 以94%的产率得到(E)-2,3-bis(phenylseleno)-2-butenedioic acid
  参考文献：
  名称：

  Free-radical additions of diselenides to dimethyl acetylenedicarboxylate, methyl propiolate, and dimethyl maleate

  摘要：

  DOI：

  10.1021/jo00246a023
• 作为产物：
  描述：

  苯基氯化硒 以 乙腈 为溶剂， 反应 4.08h， 生成 dimethyl 2,3-bis(phenylselanyl)fumarate
  参考文献：
  名称：

  Formation and electrophilic reactions of benzeneselenenyl p-toluenesulfonate. Preparation and properties of addition products with acetylenes

  摘要：

  Benzeneselenenyl p-toluenesulfonate (1) was generated in situ by the reaction of silver p-toluenesulfonate with benzeneselenenyl chloride in acetonitrile. The reagent reacted with acetylenes by electrophilic 1,2-addition to afford the beta-(phenylseleno)vinyl p-toluenesulfonates 2-12, generally in high yield. The latter were formed preferentially by anti addition, but with poor regioselectivity, unless a strongly orienting group (e.g., phenyl) was present. Selenenyl sulfonate 1 was also unexpectedly produced via radical pathways by heating p-toluenesulfonic acid with AIBN in the presence of diphenyl diselenide, or from the pyrolysis of sulfinyl sulfone 15 with the diselenide. The regioisomeric adducts 3 and 4 were prepared from 1 and 1-decyne, and both underwent elimination with potassium tert-butoxide to afford the acetylenic selenide 19 initially, which isomerized to a 6:1 mixture of the propargylic and allenic selenides 20 and 21 upon further equilibration. A Fritsch-Buttenberg-Wiechell rearrangement is proposed for the elimination of 4. The syn elimination of the selenoxide of 4 required forcing conditions and afforded only ca. 20% of the corresponding allenic sulfonate 22. The electrophile 1 induced the efficient cyclization of 5-hexen-1-ol and 4-pentenoic acid to the corresponding pyran 24 and lactone 25, respectively. It failed to cyclize alkynols, but afforded the lactones 28 and 29 from 4-pentynoic acid in low yield.

  DOI：

  10.1021/jo00008a039

文献信息

• 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。
• C–H Diselenation and Monoselenation of Electron-Deficient Alkenes via Radical Coupling at Room Temperature
  作者：Yao Chen、Mengxia Lv、Yuxin Zhang、Yao Wu、Linkun Ying、Jielin Tang、Xiangnan Gong、Jianmin Zhou、Zengqiang Song

  DOI：10.1021/acs.joc.2c01567

  日期：2022.12.16

  A new, simple, and metal-free route for the diselenation of maleimides has been first developed employing (bis(trifluoroacetoxy)iodo)benzene (PIFA) at room temperature. The present method is compatible with different functional groups, and various diselenyl maleimides were obtained in moderate to excellent yields. Moreover, this protocol further highlights the unique practical application for the functionalization

  首先开发了一种新的、简单的、无金属的马来酰亚胺脱硒途径，该途径在室温下使用（双（三氟乙酰氧基）碘）苯 (PIFA)。本方法适用于不同的官能团，并以中等至优异的收率获得了各种二硒基马来酰亚胺。此外，该协议进一步强调了生物学相关分子和氨基酸衍生物功能化的独特实际应用。初步的机制研究表明，自由基可能参与了这种新的转变。此外，该协议还适用于通过切换其他缺电子烯烃的反应条件和硒化来实现马来酰亚胺的单硒化。
• BACK, THOMAS G.;MURALIDHARAN, K. RAMAN, J. ORG. CHEM., 56,(1991) N, C. 2781-2787
  作者：BACK, THOMAS G.、MURALIDHARAN, K. RAMAN

  DOI：——

  日期：——