methyl 2-(1-oxoethyl)-6-heptenoate | 125334-60-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: methyl 2-(1-oxoethyl)-6-heptenoate
• 英文别名: 2-Acetyl-hept-6-enoic acid methyl ester；methyl 2-acetylhept-6-enoate；Methyl 2-acetyl-6-heptenoate
• CAS: 125334-60-3
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: SOWZJTHYGZXLQO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-(1-oxoethyl)-6-heptenoate 在 二甲基硫 、 sodium hydride 、 臭氧 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 15.75h， 生成 1-Ethyl methyl (+/-)-(E)-7-acetyl-7-methyl-2-nonenedioate
  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：

  5-碘-1-戊烯 、 乙酰乙酸甲酯 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 2-(1-oxoethyl)-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

• New Cobalt-Catalyzed Cycloisomerization of ε-Acetylenic β-Keto Esters. Application to a Powerful Cyclization Reactions Cascade
  作者：Paul Cruciani、Robert Stammler、Corinne Aubert、Max Malacria

  DOI：10.1021/jo9600619

  日期：1996.1.1

  type reaction of epsilon-acetylenic beta-keto esters to form highly functionalized methylenecyclopentanes are described. The observed regio-, chemo-, and stereoselectivities support a process of cycloisomerization which controls the relative stereochemistry of two contiguous stereogenic centers. An efficient route to the basic skeleton of the phyllocladane family has been achieved via a one-pot sequence

  描述了研究钴（I）催化ε-乙炔β-酮酸酯形成高度官能化的亚甲基环戊烷的烯型反应的全部细节。观察到的区域，化学和立体选择性支持环异构化的过程，该过程控制两个连续的立体发生中心的相对立体化学。通过一锅法环化序列已经实现了通往叶绿素家族基本骨架的有效途径：烯型，[2 + 2 + 2]，[4 + 2]。这种新的级联反应是从一个容易获得的无环多不饱和前体以完全立体选择性的方式产生六个碳-碳键和四个环。
• New palladium mediated cyclopentanation of alkenes bearing a δ nucleophilic substituent
  作者：Guy Fournet、Geneviève Balme、Jacques Gore

  DOI：10.1016/s0040-4039(01)80325-7

  日期：——

  A δ-alkylpalladium intermediate generated by carbopalladation of a double bond can be intramolecularly trapped by a β-diester or a β-keto ester enolate if a cyclopentane ring is formed. Otherwise, normal β-elimination is observed.

  如果形成环戊烷环，则通过双键的碳钯反应生成的δ-烷基钯中间体可能被β-二酯或β-酮酸酯烯醇化物分子内捕获。否则，观察到正常的β-消除。
• Synthesis of Various Bridged Ring Systems via Rhodium-Catalyzed Bridged (3+2) Cycloadditions
  作者：Yu-Tao He、Li-Xuan Li、Xiaohong Lin、Bao-Long Hou、Chuang-Chuang Li

  DOI：10.1021/acs.orglett.1c03837

  日期：2022.1.14

  N-sulfonyl-1,2,3-triazoles, which allowed the efficient diastereoselective construction of various functionalized and synthetically challenging bridged ring systems. This simple, direct transformation had a broad substrate scope and excellent functional group tolerance. The highly strained polycyclic bicyclo[2.2.2]octa[b]indole core of fruticosine was synthesized efficiently using this methodology.

  在这里，我们描述了N-磺酰基-1,2,3-三唑的铑催化桥接 (3+2) 环加成级联反应，这使得各种功能化和合成具有挑战性的桥接环系统的有效非对映选择性构建成为可能。这种简单、直接的转化具有广泛的底物范围和出色的官能团耐受性。使用该方法有效地合成了果糖苷的高应变多环双环[2.2.2]octa[ b ]吲哚核。
• Formation de cyclopentanes lors de réactions de Heck
  作者：Guy Fournet、Geneviève Balme、Jacques Gore

  DOI：10.1016/s0040-4020(01)90073-0

  日期：1990.1

  The Heck reaction of alkenes bearing in δ position an enolate of β-diester, βketo ester or β-sulfonyl ester leads to cyclopentanes issued from the intramolecular displacement of the carbone sp3-palladium bond by this enolate. This cyclisation is not observed when the enolate is in β or ε position or in the case of a δ-ethylenic amine and βelimination products are only obtained.

  δ位置的烯烃的Heck反应是β-二酯，β-酮酸酯或β-磺酰基酯的烯醇化物导致的环戊烷是由烯醇sp 3-钯键的分子内位移引起的。当烯醇化物处于β或ε位置或在δ-亚乙基胺的情况下，未观察到这种环化，并且仅获得β消除产物。
• A Modular Approach to α-Arylated Carbonyl Compoundsvia Indium Tris(bistriflylamide)-Catalyzed Regioselective Addition of β-Ketoesters to 1,3-Diynes
  作者：Masaharu Nakamura、Kohei Endo、Eiichi Nakamura

  DOI：10.1002/adsc.200505206

  日期：2005.10

  addition of β-keto esters to conjugated diynes and a palladium-catalyzed benzannulation reaction. Indium tris(bistriflylamide), In(NTf2)3, was found to be an efficient catalyst for the first addition reaction of β-keto esters to diynes. The reaction proceeds with perfect regioselectivity to give conjugated enynes in high yield. The second palladium-catalyzed benzannulation proceeds in high to excellent

  通过将铟催化的β-酮酯的区域选择性加成到共轭二炔上，以及钯催化的苯环化反应的组合，已经实现了α-芳基化羰基化合物的模块化合成。三（双三氟乙酰胺）铟，In（NTf 2）3发现α-酮是β-酮基酯与二炔的第一次加成反应的有效催化剂。反应以完美的区域选择性进行，以高收率得到共轭烯炔。第二种钯催化的苯并环化反应对各种二炔有很高的产率，而且具有很高的区域选择性。因此，羰基化合物的这种两步α-芳基化以催化方式进行，而不会损失原料中的元素。该反应可以在单个罐中进行，而无需分离第一步的产物。