[(E,2S)-4-nitrobut-3-en-2-yl]oxymethylbenzene | 178181-91-4

• 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: [(E,2S)-4-nitrobut-3-en-2-yl]oxymethylbenzene
• CAS: 178181-91-4
• 化学式: C₁₁H₁₃NO₃
• 分子量: 207.229
• InChiKey: YSAHLUCIRVQXGI-JARNTUPDSA-N

物化性质

• 沸点：
  334.3±30.0 °C(Predicted)
• 密度：
  1.120±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [(4-Chlorophenyl)-(3,4,5-trimethyl-1,3-thiazol-3-ium-2-yl)methoxy]-triethylsilane;iodide 、 [(E,2S)-4-nitrobut-3-en-2-yl]oxymethylbenzene 在 四甲基氟化铵 、 N,N'-二苯基硫脲 作用下， 以 二氯甲烷 为溶剂， 以80 mg的产率得到3-(benzyloxy)-1-(4-chlorophenyl)-2-(nitromethyl)butan-1-one
  参考文献：
  名称：

  氟化物阴离子/硫脲组合促进硝基烯烃的直接亲核酰化

  摘要：

  据报道，硝基烯烃的直接亲核酰化是利用受保护的噻唑鎓甲醇的氟化物引发的重排。氟阴离子和硫脲的关键组合可在不使用生成这些 Umpolung 亲核试剂时通常使用的胺或酰胺碱的情况下获得羰基阴离子反应性。用于原位生成反应性羰基阴离子物质的温和反应条件允许以良好的产率将共轭添加物添加到敏感的硝基烯烃亲电试剂中。该方法耐受多种噻唑鎓甲醇和硝基烯烃底物，并且可以通过添加源自奎宁的手性硫脲来赋予对映选择性和非对映选择性。

  DOI：

  10.1021/ja056565i
• 作为产物：
  描述：

  (S)-2-苄氧基丙醛 在 甲基磺酰氯 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 反应 3.0h， 生成 [(E,2S)-4-nitrobut-3-en-2-yl]oxymethylbenzene
  参考文献：
  名称：

  Stereocontrolled Synthesis of Highly Substituted Proline Esters via [3 + 2] Cycloaddition between N-Metalated Azomethine Ylides and Nitroalkenes. Origins of the Metal Effect on the Stereochemical Outcome

  摘要：

  The [3 + 2] cycloaddition reaction between several N-metalated azomethine ylides and nitroalkenes has been studied using AgOAc and LiClO4 as metalating reagents in the presence of triethylamine. The reaction is found to be very versatile and can be extended to homochiral nitroalkenes. In general, lithium and silver salts promote preferential formation of the endo and exo cycloadducts, respectively. The presence of a phenol moiety induces a shift toward the exo-cycloadduct even when lithium is used. A model based upon the experimental results obtained and SCF-MO calculations is proposed to explain the variable stereochemical outcome of these reactions.

  DOI：

  10.1021/jo971212q

文献信息

• 4M lithium perchlorate-nitromethane: An efficient solvent in Diels-Alder reactions using nitroalkenes as dienophiles
  作者：Mirari Ayerbe、Fernando P. Cossío

  DOI：10.1016/0040-4039(95)00678-6

  日期：1995.6

  Diels-Alder reactions in which nitroalkenes act as dienophiles are substantially accelerated in 4M lithium perchlorate-nitromethane solutions. This acceleration is higher than that observed when the known 5M lithium perchlorate-diethyl ether system is used.

  在4M高氯酸锂-硝基甲烷溶液中，硝基烯烃充当亲二烯体的Diels-Alder反应得到了显着加速。该加速度高于使用已知的5M高氯酸锂-乙醚系统观察到的加速度。
• Stereoselective conjugate addition of carbon nucleophiles to chiral (E)-nitroalkenes bearing a γ-stereocenter. Origins of the observed anti selectivity
  作者：Mirari Ayerbe、Iñaki Morao、Ana Arrieta、Anthony Linden、Fernando P. Cossio

  DOI：10.1016/0040-4039(96)00468-6

  日期：1996.4

  The reaction between different organometallic carbon nucleophiles and chiral (E)-nitroalkenes has been studied. Anti selectivities have been observed in all cases. SCF-MO calculations suggest that the observed stereocontrol relies on the anti disposition of a donor group (methyl or hydrogen) with respect to the CC bond in formation.

  研究了不同有机金属碳亲核试剂与手性（E）-硝基烯烃之间的反应。在所有情况下均观察到抗选择性。SCF-MO的计算表明，所观察到的立体控制依赖于反相对于在形成CC键的供体基团（甲基或氢）的处置。
• Stereocontrolled Synthesis of Highly Substituted Proline Esters via [3 + 2] Cycloaddition between N-Metalated Azomethine Ylides and Nitroalkenes. Origins of the Metal Effect on the Stereochemical Outcome
  作者：Mirari Ayerbe、Ana Arrieta、Fernando P. Cossío、Anthony Linden

  DOI：10.1021/jo971212q

  日期：1998.3.1

  The [3 + 2] cycloaddition reaction between several N-metalated azomethine ylides and nitroalkenes has been studied using AgOAc and LiClO4 as metalating reagents in the presence of triethylamine. The reaction is found to be very versatile and can be extended to homochiral nitroalkenes. In general, lithium and silver salts promote preferential formation of the endo and exo cycloadducts, respectively. The presence of a phenol moiety induces a shift toward the exo-cycloadduct even when lithium is used. A model based upon the experimental results obtained and SCF-MO calculations is proposed to explain the variable stereochemical outcome of these reactions.
• Direct Nucleophilic Acylation of Nitroalkenes Promoted by a Fluoride Anion/Thiourea Combination
  作者：Anita E. Mattson、Andrea M. Zuhl、Troy E. Reynolds、Karl A. Scheidt

  DOI：10.1021/ja056565i

  日期：2006.4.1

  carbonyl anion species in situ allow for conjugate additions in good yield to sensitive nitroalkene electrophiles. The process is tolerant of a variety of thiazolium carbinols and nitroalkene substrates and can be rendered enantioselective and diastereoselective by the addition of a chiral thiourea derived from quinine.

  据报道，硝基烯烃的直接亲核酰化是利用受保护的噻唑鎓甲醇的氟化物引发的重排。氟阴离子和硫脲的关键组合可在不使用生成这些 Umpolung 亲核试剂时通常使用的胺或酰胺碱的情况下获得羰基阴离子反应性。用于原位生成反应性羰基阴离子物质的温和反应条件允许以良好的产率将共轭添加物添加到敏感的硝基烯烃亲电试剂中。该方法耐受多种噻唑鎓甲醇和硝基烯烃底物，并且可以通过添加源自奎宁的手性硫脲来赋予对映选择性和非对映选择性。