Methyl (+/-)-2-(ethoxycarbonyl)-6-heptenoate | 153165-69-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Methyl (+/-)-2-(ethoxycarbonyl)-6-heptenoate
• 英文别名: 1-ethyl 3-methyl 2-(pent-4-en-1-yl)malonate；1-O-ethyl 3-O-methyl 2-pent-4-enylpropanedioate
• CAS: 153165-69-6
• 化学式: C₁₁H₁₈O₄
• 分子量: 214.262
• InChiKey: VRENSPNDWFCELY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 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 (+/-)-2-(ethoxycarbonyl)-6-heptenoate 在 二甲基硫 、 sodium hydride 、 臭氧 、 lithium chloride 作用下， 以 六甲基磷酰三胺 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 19.75h， 生成 Ethyl (+/-)-(1R*,2S*)-2-(ethoxycarbonyl)-2-methylcyclopentane-1-acetate
  参考文献：
  名称：

  Functionalized carbocycles by tandem dealkoxycarbonylation-Michael addition reactions

  摘要：

  A tandem dealkoxycarbonylation-Michael addition reaction has been developed as a synthetic route to highly functionalized carbocycles. Methyl esters, activated toward decarboxylation by an electron-withdrawing group at C-2 and tethered by a three- or four-carbon chain to an acrylate Michael acceptor, have been prepared and used as the cyclization substrates. Treatment of these compounds with LiCl in HMPA at 120-degrees-C or 4 h results in selective S(N)2 dealkylation of the methyl esters, decarboxylation, and cyclization of the intermediate anions by a Michael addition to the pendant acrylate moiety. This affords 45-90% of the cyclopentane- and cyclohexaneacetic esters substituted at C-2 by an electron-with drawing group. Moderate to excellent selectivity (3:1-99:1) in favor of the product having the electron-withdrawing group trans to the acetic ester side chain is observed. The reaction works best for the preparation of five-membered rings, and cyclizations proceed most cleanly from substrates which cyclize through a tertiary carbanion. Synthetic and mechanistic details as well as optimization studies and product structure proofs are presented.

  DOI：

  10.1021/jo00077a043
• 作为产物：
  描述：

  ethyl methyl malonate 、 5-溴-1-戊烯 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以84%的产率得到Methyl (+/-)-2-(ethoxycarbonyl)-6-heptenoate
  参考文献：
  名称：

  Functionalized carbocycles by tandem dealkoxycarbonylation-Michael addition reactions

  摘要：

  A tandem dealkoxycarbonylation-Michael addition reaction has been developed as a synthetic route to highly functionalized carbocycles. Methyl esters, activated toward decarboxylation by an electron-withdrawing group at C-2 and tethered by a three- or four-carbon chain to an acrylate Michael acceptor, have been prepared and used as the cyclization substrates. Treatment of these compounds with LiCl in HMPA at 120-degrees-C or 4 h results in selective S(N)2 dealkylation of the methyl esters, decarboxylation, and cyclization of the intermediate anions by a Michael addition to the pendant acrylate moiety. This affords 45-90% of the cyclopentane- and cyclohexaneacetic esters substituted at C-2 by an electron-with drawing group. Moderate to excellent selectivity (3:1-99:1) in favor of the product having the electron-withdrawing group trans to the acetic ester side chain is observed. The reaction works best for the preparation of five-membered rings, and cyclizations proceed most cleanly from substrates which cyclize through a tertiary carbanion. Synthetic and mechanistic details as well as optimization studies and product structure proofs are presented.

  DOI：

  10.1021/jo00077a043

文献信息

• Intramolecular palladium-catalyzed alkene carboalkynylation
  作者：Stefano Nicolai、Peter Swallow、Jerome Waser

  DOI：10.1016/j.tet.2015.06.030

  日期：2015.9

  Carbocycles are essential building blocks for the synthesis of natural and synthetic bioactive compounds. Herein, we report the first example of palladium-catalyzed intramolecular carboalkynylation of non-activated olefins. Using activated carbonyl compounds as nucleophiles and an alkynyl bromide as an electrophile, the reaction gives access to cyclopentanes in 44-93% yield and one example of cyclohexane in 31% yield with simultaneous formation of a SP3-SP C-C bond. The reaction therefore combines ring formation with the introduction of a versatile triple bond for further functionalization. (C) 2015 Elsevier Ltd. All rights reserved.
• Functionalized carbocycles by tandem dealkoxycarbonylation-Michael addition reactions
  作者：Richard A. Bunce、Eric D. Dowdy、Paul B. Jones、Elizabeth M. Holt

  DOI：10.1021/jo00077a043

  日期：1993.12

  A tandem dealkoxycarbonylation-Michael addition reaction has been developed as a synthetic route to highly functionalized carbocycles. Methyl esters, activated toward decarboxylation by an electron-withdrawing group at C-2 and tethered by a three- or four-carbon chain to an acrylate Michael acceptor, have been prepared and used as the cyclization substrates. Treatment of these compounds with LiCl in HMPA at 120-degrees-C or 4 h results in selective S(N)2 dealkylation of the methyl esters, decarboxylation, and cyclization of the intermediate anions by a Michael addition to the pendant acrylate moiety. This affords 45-90% of the cyclopentane- and cyclohexaneacetic esters substituted at C-2 by an electron-with drawing group. Moderate to excellent selectivity (3:1-99:1) in favor of the product having the electron-withdrawing group trans to the acetic ester side chain is observed. The reaction works best for the preparation of five-membered rings, and cyclizations proceed most cleanly from substrates which cyclize through a tertiary carbanion. Synthetic and mechanistic details as well as optimization studies and product structure proofs are presented.