ethyl 3-methoxycyclohepta-1,3,5-triene-7-carboxylate | 850934-79-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 3-methoxycyclohepta-1,3,5-triene-7-carboxylate
• 英文别名: ethyl 4-methoxycyclohepta-2,4,6-triene-1-carboxylate；ethyl 4-methoxy-2,4,6-cycloheptatrienecarboxylate；2,4,6-Cycloheptatriene-1-carboxylic acid, 4-methoxy-, ethyl ester
• CAS: 850934-79-1
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: GICJDJWWNXVEFH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 3-methoxycyclohepta-1,3,5-triene-7-carboxylate 在 barium(II) hydroxide 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以89%的产率得到5-Methoxycyclohepta-1,3,5-triene-1-carboxylic acid
  参考文献：
  名称：

  使用顺序环加成获得 Welwitindolinone 核心

  摘要：

  在顺序环加成反应的基础上，开发了一种对 welwitindolinone 生物碱核心骨架的简明方法。首先，使用钯催化的对映选择性 [6 + 3] 三亚甲基甲烷环加成到托酮核上以生成必需的双环 [4.3.1] 癸二烯。随后对环加合物的修改允许分子内 [4 + 2] 环加成生成羟吲哚并完成天然产物家族的核心。

  DOI：

  10.1021/ol901499b
• 作为产物：
  描述：

  重氮乙酸乙酯 、 苯甲醚 生成 ethyl 3-methoxycyclohepta-1,3,5-triene-7-carboxylate
  参考文献：
  名称：

  甲氧基取代的光学活性 7-烷氧基羰基环庚三烯的制备及其酸促重排

  摘要：

  四种在不同位置带有甲氧基的旋光环庚三烯衍生物是通过 2,4-戊二醇-栓系布氏反应制备的。除了高立体选择性外，系链还以从良好到高度的方式控制区域选择性。一些产品在酸性条件下不稳定，通过质子反应或芳构化导致异构化。布朗斯台德酸通过区域和立体选择性质子化和随后的去质子化促进质子异构化，而路易斯酸催化的反应通过去甲卡二烯互变异构体提供芳构化产物。

  DOI：

  10.1246/bcsj.78.671

文献信息

• Regioselective and Enantioselective Intermolecular Buchner Ring Expansions in Flow
  作者：Gabrielle S. Fleming、Aaron B. Beeler

  DOI：10.1021/acs.orglett.7b02537

  日期：2017.10.6

  The first example of a regioselective and enantioselective intermolecular Buchner ring expansion is reported using continuous flow. The practicality and scope of the reaction are greatly improved under flow conditions. Reactions of ethyl diazoacetate with symmetric and nonsymmetric arenes afford cycloheptatrienes in good yield and excellent regioselectivity. The first example of an asymmetric intermolecular

  使用连续流动报道了区域选择性和对映选择性分子间布氏环膨胀的第一个例子。在流动条件下，反应的实用性和范围得到了极大的改善。重氮乙酸乙酯与对称和不对称芳烃的反应以良好的收率和优异的区域选择性提供了环庚烯。不对称分子间布氏反应的第一个例子已证明对二取代重氮酯具有良好的至优异的对映选择性。不对称反应以绝对的区域选择性进行，得到具有全碳季中心的环庚烯。
• Kinetic Separation and Asymmetric Reactions of Norcaradiene Cycloadducts: Facilitated Access via H₂O-Accelerated Cycloaddition
  作者：William D. Mackay、Jeffrey S. Johnson

  DOI：10.1021/acs.orglett.5b03577

  日期：2016.2.5

  We exploit the Buchner reaction to access 1,2-disubstituted cyclohexadiene synthons (norcaradienes), which participate in H2O-accelerated cycloaddition with dieneophiles to provide cyclopropyl-fused [2.2.2]-bicyclooctene derivatives in good yields. Regioisomeric mixtures can be kinetically separated by exploiting different reaction rates in Diels Alder reactions. Meso-Diels-Alder products may be enantioselectively desymmetrized, providing highly substituted cyclohexanes with up to seven contiguous stereocenters.
• Büchner Reactions Catalyzed by a Silver(I) Pyridylpyrrolide: Understanding Arene C═C Insertion Selectivity
  作者：Nobuyuki Komine、Jaime A. Flores、Kuntal Pal、Kenneth G. Caulton、Daniel J. Mindiola

  DOI：10.1021/om301240d

  日期：2013.6.10

  The complex Ag-3(mu(2)-3,5-(CF3)(2)PyrPy)(3) (3,5-(CF3)(2)PyrPy = 2,2'-pyridylpyrrolide(1-) ligand) catalytically promotes the insertion of the carbene of ethyl diazoacetate (EDA), at room temperature, into the C=C bond of a series of arenes to ultimately ring-open them and form the corresponding cycloheptatrienes. In one case, the norcaradiene intermediate can be isolated, while regioselective C=C insertion can be promoted with certain arene substrates. The mechanism of C=C insertion, preference over C-H insertion, and origin of C=C regioselectivity has been probed by a combination of experimental and theoretical studies.
• A silver-catalyzed Büchner reaction
  作者：Carl J. Lovely、R. Greg Browning、Vivek Badarinarayana、H.V. Rasika Dias

  DOI：10.1016/j.tetlet.2005.02.052

  日期：2005.4

  A silver scorpionate complex, derived from the highly fluorinated [HB(3,5-(CF3)(2)PZ)3](-), catalyzes the addition of ethyl diazoacetate to benzene rings, providing norcaradienes, which undergo elect rocyclization to provide the corresponding cycloheptatriene. These reactions are surprisingly selective for addition to the aromatic moiety rather than C-H insertion. (c) 2005 Elsevier Ltd. All rights reserved.
• Preparation of Methoxy-Substituted Optically Active 7-Alkoxycarbonylcycloheptatrienes and Their Acid-Promoted Rearrangements
  作者：Takashi Sugimura、Masami Kagawa、Naoko Ohuchi、Kazutake Hagiya、Tadashi Okuyama

  DOI：10.1246/bcsj.78.671

  日期：2005.4

  Four optically active cycloheptatriene derivatives carrying a methoxy group(s) at different positions were prepared by the 2,4-pentanediol-tethered Buchner reaction. In addition to the high stereoselectivity, the tetheralso controlled the regioselectivity in a good-to-high degree. Some of the products are unstable under acidic conditions, resulting in isomerization through a prototropic reaction or aromatization

  四种在不同位置带有甲氧基的旋光环庚三烯衍生物是通过 2,4-戊二醇-栓系布氏反应制备的。除了高立体选择性外，系链还以从良好到高度的方式控制区域选择性。一些产品在酸性条件下不稳定，通过质子反应或芳构化导致异构化。布朗斯台德酸通过区域和立体选择性质子化和随后的去质子化促进质子异构化，而路易斯酸催化的反应通过去甲卡二烯互变异构体提供芳构化产物。