4-(benzoyloxy)-2-methyl-3-nitro-1-butene | 134916-28-2

• 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: 4-(benzoyloxy)-2-methyl-3-nitro-1-butene
• 英文别名: 1-benzyloxy-3-methyl-2-nitrobut-3-ene；(3-Methyl-2-nitrobut-3-enyl) benzoate
• CAS: 134916-28-2
• 化学式: C₁₂H₁₃NO₄
• 分子量: 235.24
• InChiKey: ZTCCXXPBSCSLHP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-(benzoyloxy)-2-methyl-3-nitro-1-butene 在 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 6-ethoxy-3a-prop-1-en-2-yl-3,4,5,6-tetrahydro-2H-[1,2]oxazolo[2,3-b]oxazine-2-carbonitrile
  参考文献：
  名称：

  3-取代的-2-硝基-1,3-二烯的生成和环加成反应。

  摘要：

  已经开发了两种用于区域特异性制备3-取代的-2-硝基-1，3-二烯的方法。已经研究了原位生成的二烯的环加成化学。

  DOI：

  10.1016/s0040-4039(00)74370-x
• 作为产物：
  描述：

  3-methyl-2-nitro-3-buten-1-ol 、 苯甲酰氯 以 苯 为溶剂， 生成 4-(benzoyloxy)-2-methyl-3-nitro-1-butene
  参考文献：
  名称：

  A new enantioselective route to kainoids: application to the formal synthesis of (–)-α-kainic acid

  摘要：

  通过以 2-硝基-3-甲基丁-1,3-二烯为亲电烯烃的串联迈克尔反应策略，完成了一种 2,3,4-三取代吡咯烷的对映选择性合成，该吡咯烷具有凯氏 C-2、C-3 反式、C-3、C-4 顺式排列的取代基、可拆卸的抽电子基团可作为控制环化立体化学的模板，再加上在含氮亲核碳上含有手性中心的仲苄胺和能够捕获最初形成的硝酸酯的δ,δ-不饱和受体。

  DOI：

  10.1039/c39910000390

文献信息

• Generation and cycloaddition reactions of substituted 2-nitro-1,3-dienes
  作者：Achille Barco、Simonetta Benetti、Carmela De Risi、Carlo F. Morelli、Gian P. Pollini、Vinicio Zanirato

  DOI：10.1016/0040-4020(96)00476-0

  日期：1996.7

  by suitable partners such as methyl acrylate, cyclopentadiene or ethyl vinyl ether. The expected cycloadducts are regiochemically formed by reaction with methyl acrylate, while the initially formed adducts with cyclopentadiene underwent thermal Cope or hetero-Cope rearrangements leading to the formation of nitro-substituted bicyclic compounds. The thermal rearrangement of the oxazine-N-oxides resulting

  4-酰氧基-2-取代的-3-硝基-1-丁烯已被用作相应的2-硝基-3-取代的1,3-丁二烯的方便前体，这些原位很容易就地产生。通过加热或用乙酸钠处理并被合适的伴侣如丙烯酸甲酯，环戊二烯或乙基乙烯基醚截留。预期的环加合物是通过与丙烯酸甲酯反应在区域化学上形成的，而最初形成的与环戊二烯的加合物经历了热Cope或杂Cope重排，从而导致了硝基取代的双环化合物的形成。通过异狄尔斯-阿尔德反应与乙基乙烯基醚作为环加成伙伴的异嗪-N-氧化物的热重排导致形成1,2-恶唑-3-丙醛。通过使用这些多偶联试剂而产生的多种高度官能化的碳环和杂环化合物为构建简单和复杂的天然化合物提供了有用的合成子。
• A new approach to kainoids through tandem Michael reaction methodology: application to the enantioselective synthesis of (+)- and (-)-.alpha.-allokainic acid and to the formal synthesis of (-)-.alpha.-kainic acid
  作者：Achille Barco、Simonetta Benetti、Giampiero Spalluto、Alberto Casolari、Gian P. Pollini、Vinicio Zanirato

  DOI：10.1021/jo00049a040

  日期：1992.11

  A convergent, one-pot construction of functionalized pyrrolidine ring systems has been developed. The method is based on a tandem Michael reaction initiated by an intermolecular conjugate addition of a nitrogen nucleophile to an electrophilic olefin followed by trapping of the generated enolate by a built-in alpha,beta-unsaturated acceptor. After model studies verified the feasibility of the process and gave information about its stereochemical outcome, the strategy was successfully applied to kainoid synthesis. The construction of the basic pyrrolidine skeleton of all the members of the family requires coupling of a suitable electrophilic subunit with a common donor-acceptor fragment containing the nitrogen nucleophile. Thus, the enantioselective synthesis of (+)-alpha-allokainic acid (2) and the formal synthesis of its C-4 epimer (-)-alpha-kainic acid (1), have been accomplished using methyl vinyl ketone and 2-nitro-3-methyl-1,3-butadiene, respectively, as electrophilic partners of (S)-4-(benzylamino)-5-hydroxy-2-pentenoic acid ethyl ester (17), easily derived in six steps from D-serine. Although the acetyl group of methyl vinyl ketone is a logical precursor to the isopropenyl moiety of 2, the use of the nitrobutadiene is more appropriate for the synthesis of 1 because of the startling degree of control of the cyclization stereochemistry exerted by the nitro group.