methyl (E)-4-(2-formylphenoxy)but-2-enoate | 28809-07-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: methyl (E)-4-(2-formylphenoxy)but-2-enoate
• 英文别名: (E)-methyl 4-(2-formylphenoxy)but-2-enoate；(e)-Methyl 4-(2-formylphenoxy) but-2-enoate
• CAS: 28809-07-6
• 化学式: C₁₂H₁₂O₄
• 分子量: 220.225
• InChiKey: UDALHVUWSFOPSC-QPJJXVBHSA-N

物化性质

• 熔点：
  62-64 °C
• 沸点：
  367.2±27.0 °C(Predicted)
• 密度：
  1.169±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  methyl (E)-4-(2-formylphenoxy)but-2-enoate 在 o-(o-Tol)2P-C₆H₄-((S)-4-i-Pr-5,5-Ph₂-4,5-H₂-oxazol-2-yl) 、 silver(I) acetate 、 magnesium sulfate 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 6.0h， 生成 (+)-1,2,3,3a,4,9b-hexahydro-5-oxa-1-azacyclopenta[a]naphthalene-2,3-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Enantio- and Diastereoselective [3+2] Cycloadditions of Azomethine Ylides with Ag(I)-Phosphinooxazoline Catalysts

  摘要：

  手性 Ag(I)-phosphinooxazoline (PHOX) 复合物是偶氮甲基酰化物与δ,δ-不饱和羧酸酯发生 [3+2] 环加成反应的高效催化剂。在分子内环加成反应中，几乎完全实现了非对映控制，对映体过量率高达 99%。

  DOI：

  10.1055/s-2005-865313
• 作为产物：
  描述：

  顺丁烯二酸单甲酯 在 硼烷四氢呋喃络合物 、 potassium carbonate 、 三乙胺 、 potassium bromide 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 2.75h， 生成 methyl (E)-4-(2-formylphenoxy)but-2-enoate
  参考文献：
  名称：

  Microwave-assisted solvent-free intramolecular 1,3-dipolar cycloaddition reactions leading to hexahydrochromeno[4,3-b]pyrroles: scope and limitations

  摘要：

  We report the microwave-assisted solvent-free synthesis of hexahydrochromeno[4,3-b]pyrroles. Intramolecular 1,3-dipolar cycloadditions proceed under these conditions within 15-40 min in 16-84% yields. An influence of the microwave irradiation upon various [3+2] cycloaddition reaction intermediates was studied. Additionally, a scope and limitations of these reactions including an influence of the dipolarophile geometry upon the cycloaddition selectivity and steric demands of the dipole upon its reactivity were also disclosed. These observations led us to postulate a preferable transition state of the reaction. Finally, an influence of the microwave irradiation to the isomerization of activated olefins was also described. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.10.074

文献信息

• An Efficient and Versatile Approach for the Immobilization of Carbene Precursorsvia Copper-Catalyzed [3+2]-Cycloaddition and their Catalytic Application
  作者：Kirsten Zeitler、Ina Mager

  DOI：10.1002/adsc.200700174

  日期：2007.8.6

  azide-functionalized support via copper-catalyzed 1,3-dipolar cycloaddition, which efficiently yields a rigid and robust 1,2,3-triazole linkage. The catalytic performance of the corresponding nucleophilic carbenes (NHCs) was examined in intramolecular Stetter reactions (chroman-4-one products) and organocatalytic redox esterifications (α,β-unsaturated esters). The MeOPEG-immobilized organocatalysts are

  可以通过铜催化的1,3-偶极环加成将不同种类的炔基取代的杂唑衍生物共价固定在叠氮化物官能化的支持物上，这有效地产生了刚性且牢固的1,2,3-三唑键。在分子内Stetter反应（苯并四氢呋喃产物）和有机催化氧化还原酯化反应（α，β-不饱和酯）中检查了相应亲核碳烯（NHC）的催化性能。固定有MeOPEG的有机催化剂具有很高的活性，并显示出与非负载衍生物相当的非对映选择性。此外，它们还简化了后处理程序，并且已被证明可回收利用。
• Exploring O-stannyl ketyl and acyl radical cyclizations for the synthesis of γ-lactone-fused benzopyrans and benzofurans
  作者：Helen Santoso、Myriam I. Casana、Christopher D. Donner

  DOI：10.1039/c3ob42090f

  日期：——

  The synthesis of a series of γ-lactone-fused benzopyrans and benzofurans, analogues of the pyranonaphthoquinone antibiotics, is reported. Preparation of the heterocycles was achieved by either O-stannyl ketyl or acyl radical cyclization of benzaldehyde precursors followed by oxidation to give the pyrano- and furanobenzoquinone systems. The observed diastereoselectivity during O-stannyl ketyl radical

  据报道，合成了一系列γ-内酯融合的苯并吡喃和苯并呋喃，它们是吡喃并萘醌抗生素的类似物。杂环的制备是通过苯甲醛前体的O-锡烷基酮基或酰基自由基环化，然后氧化得到吡喃基和呋喃基苯醌体系而实现的。O-锡烷基酮基自由基环化过程中观察到的非对映选择性受醛的芳族取代邻位的影响，而酰基自由基环化然后立体选择性还原所得吡喃酮提供了形成所需的γ-内酯融合的苯并吡喃体系的补充方法。
• Nitrile Oxide [3 + 2] Cycloaddition: Application to the Synthesis of 6-Substituted 3(2<i>H</i>)-Pyridazinones and 6-Substituted 4,5-Dihydro-4-hydroxy-3(2<i>H</i>)-pyridazinones
  作者：P. G. Baraldi、A. Bigoni、B. Cacciari、C. Caldari、S. Manfredini、G. Spalluto

  DOI：10.1055/s-1994-25663

  日期：——

  An efficient method for the preparation of 6-substituted 3(2H)-pyridazinones and 6-substituted 4,5-dihydro-4-hydroxy-3(2H)-pyridazinones starting from 3,5-disubstituted 4,5-dihydroisoxazoles is described. N-O bond cleavage of the isoxazoline ring promoted by molybdenum hexacarbonyl or by catalytic hydrogenation afforded the α-hydroxy γ-keto esters 4a-f which were converted into 6-substituted 4,5-dihydro-4-hydroxy-3(2H)-pyridazinones 5a-f or 6-substituted 3(2H)-pyridazinones 6a-f on treatment with hydrazine hydrate at room temperature or reflux in high yield starting from 4a-f. The flexibility of this protocol has been demonstrated by the synthesis of the C-nucleoside 7 starting from the known β-ribofu-ranosylnitromethane 8. Moreover, an intramolecular version of this methodology has been developed to prepare the known antiulcer tricyclic 3(2H)-pyridazinone 12.

  描述了一种从3,5-二取代的4,5-二氢异噁唑出发，高效制备6-取代的3(2H)-吡嗪酮和6-取代的4,5-二氢-4-羟基-3(2H)-吡嗪酮的方法。通过六羰基钼或催化氢化促进异噁唑啉环的N-O键断裂，获得了α-羟基γ-酮酯4a-f，这些酯在室温或回流条件下与水合肼反应生成6-取代的4,5-二氢-4-羟基-3(2H)-吡嗪酮5a-f或6-取代的3(2H)-吡嗪酮6a-f，且收率较高。该协议的灵活性通过从已知的β-核糖硝基甲烷8合成C-核糖苷7得到了验证。此外，还开发了一种分子内版本的方法来制备已知的抗溃疡三环3(2H)-吡嗪酮12。
• Post-Ugi Cascade Transformations for Accessing Diverse Chromenopyrrole Collections
  作者：Vunnam Srinivasulu、Scott McN. Sieburth、Raafat El-Awady、Noor M. Kariem、Hamadeh Tarazi、Matthew John O’Connor、Taleb H. Al-Tel

  DOI：10.1021/acs.orglett.7b03986

  日期：2018.2.2

  serendipitous one-pot protocol for the diastereoselective construction of diverse collections of chromenopyrroles is described. This methodology features an unprecedented five-step cascade including azomethine ylide generation followed by in situ intramolecular [3 + 2]-cycloaddition. Furthermore, this protocol was extended to access enantiopure chromenopyrroles using amino acids as chiral auxiliary.

  利用构建/耦合/配对策略，描述了一个偶然的一锅协议，用于非对映选择性构建不同种类的苯并吡咯。该方法具有前所未有的五步级联反应，包括生成甲亚胺叶立德，然后进行原位分子内[3 + 2]-环加成反应。此外，该协议已扩展为使用氨基酸作为手性助剂来获得对映纯的色吡咯。此外，使用配对后反应来增加我们的试验化合物集合的多样性和复杂性。
• Nonstabilized Azomethine Ylides Generated by Decarboxylative Condensation of α-Amino Acids. Structural Variation, Reactivity, and Stereoselectivity
  作者：Shuji Kanemasa、Kazushige Sakamoto、Otohiko Tsuge

  DOI：10.1246/bcsj.62.1960

  日期：1989.6

  A variety of aldehydes, containing enolizable aldehydes other than acetaldehyde can be used in the generation method of nonstabilized azomethine ylides by decarboxylative condensation of α-amino acids. Reactivity of the nonstabilized ylides was examined in intermolecular and intramolecular cycloadditions with olefins; stereoselectivity of the intramolecular cycloaddition using nonstabilized ylides was compared with that of ester-stabilized ylides.

  可以使用多种醛类，除了乙醛之外的可烯醇化醛，来通过 α-氨基酸的脱羧缩合生成非稳定的亚胺阳离子。非稳定阳离子的反应性在与烯烃的分子间和分子内环加成反应中进行了研究；使用非稳定阳离子的分子内环加成反应的立体选择性与酯稳定阳离子的立体选择性进行了比较。

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