Methyl 4-(2-oxocyclohexyl)-2-butynoate | 172978-12-0

• 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 4-(2-oxocyclohexyl)-2-butynoate
• 英文别名: 2-Butynoic acid, 4-(2-oxocyclohexyl)-, methyl ester；methyl 4-(2-oxocyclohexyl)but-2-ynoate
• CAS: 172978-12-0
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: MFQJMXOABWNIBS-UHFFFAOYSA-N

物化性质

• 沸点：
  331.8±15.0 °C(Predicted)
• 密度：
  1.098±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 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 4-(2-oxocyclohexyl)-2-butynoate 在 三甲基氯硅烷 、 四氯化钛 、 lithium 、 cesium fluoride 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以90%的产率得到(4,5,6,7-Tetrahydro-1H-indol-2-yl)-acetic acid methyl ester
  参考文献：
  名称：

  固定大气氮：以大气氮为氮源合成杂环。

  摘要：

  干燥的空气是与TiL 4，Li和TMSC1反应的分子氮源（L = Cl，OiPr； TMS =三甲基甲硅烷基）。这样制得的氮钛配合物可用于由羰基化合物合成吲哚，吡咯和内酰胺。将此方法应用于1可以访问2，这是合成（±）-番茄红素的关键化合物。

  DOI：

  10.1002/(sici)1521-3773(19980316)37:5<636::aid-anie636>3.0.co;2-x
• 作为产物：
  描述：

  4-氯-2-丁炔酸甲酯 、 1-环己烯氧基三甲基硅烷 生成 Methyl 4-(2-oxocyclohexyl)-2-butynoate
  参考文献：
  名称：

  Propargyl Chlorides as Sources for Cobalt Stabilized .gamma.-Carbonyl Cations

  摘要：

  Hexacarbonyldicobalt complexes of gamma-chloroalkynones and gamma-chloroalkynoates (5) were found to undergo silver-mediated Nicholas condensation reactions with silyl enol ethers or silyl ketene acetals (10) to give 1,6-dicarbonyl complexes 11 in fair to good yields. Substrates 5 with gamma-alkyl substitution formed diastereomeric products with enol silanes 10a and 10b. Reactions with propiophenone trimethylsilyl enol ether (10b) gave good levels of syn diastereoselection, whereas reactions with cyclohexanone trimethylsilyl enol ether (10a) were only slightly diastereoselective, favoring the anti diastereomer. When conducted in acetonitrile, the silver-mediated reaction of 5e gave a radical dimerization product 13, isolated as the syn diastereomer.

  DOI：

  10.1021/jo00128a022

文献信息

• Fixation of Atmospheric Nitrogen: Synthesis of Heterocycles with Atmospheric Nitrogen as the Nitrogen Source
  作者：Miwako Mori、Katsutoshi Hori、Masaya Akashi、Masanori Hori、Yoshihiro Sato、Mayumi Nishida

  DOI：10.1002/(sici)1521-3773(19980316)37:5<636::aid-anie636>3.0.co;2-x

  日期：1998.3.16

  Dry air is the source of molecular nitrogen for reactions with TiL4 , Li, and TMSCl (L = Cl, OiPr; TMS = trimethylsilyl). The nitrogen-titanium complexes thus prepared can be used to synthesize indoles, pyrroles, and lactams from carbonyl compounds. Applying this method to 1 provides access to 2, the key compound in the synthesis of (±)-lycopodine.

  干燥的空气是与TiL 4，Li和TMSC1反应的分子氮源（L = Cl，OiPr； TMS =三甲基甲硅烷基）。这样制得的氮钛配合物可用于由羰基化合物合成吲哚，吡咯和内酰胺。将此方法应用于1可以访问2，这是合成（±）-番茄红素的关键化合物。
• Synthesis of Tetrahydroindole Derivatives Using Titanium-Nitrogen Complexes Derived from Molecular Nitrogen
  作者：Masaya Akashi、Mayumi Nishida、Miwako Mori

  DOI：10.1246/cl.1999.465

  日期：1999.6

  Synthesis of tetrahydroindole derivatives was realized from keto-alkyne using titanium-nitrogen complexes generated from Ti(OiPr)4, Li, and TMSCl. In this reaction, the electron-withdrawing group on the alkyne gave a good yield, and keto-alkynes having an aromatic ring on the alkyne also gave tetrahydroindole derivatives in good to moderate yields.

  使用由 Ti(OiPr)4、Li 和 TMSCl 生成的钛-氮配合物，从酮-炔烃合成四氢吲哚衍生物。在该反应中，炔烃上的吸电子基团产生了良好的产率，炔烃上具有芳环的酮基炔烃也以良好至中等的产率得到了四氢吲哚衍生物。
• Akashi, Masaya; Mori, Miwako, Heterocycles, 2003, vol. 59, # 2, p. 661 - 668
  作者：Akashi, Masaya、Mori, Miwako

  DOI：——

  日期：——
• Nitrogen Fixation: Synthesis of Heterocycles Using Molecular Nitrogen as a Nitrogen Source
  作者：Miwako Mori、Masaya Akashi、Masanori Hori、Katsutoshi Hori、Mayumi Nishida、Yoshihiro Sato

  DOI：10.1246/bcsj.77.1655

  日期：2004.9

  Nitrogen fixation using transition metals is a fascinating process. We have already reported on the incorporation of molecular nitrogen into organic compounds using a titanium–nitrogen complex reported by Yamamoto. We developed a novel titanium-catalyzed nitrogenation procedure using TiCl4 in the presence of an excess amount of Li and TMSCl. In this reaction, a 1 atm pressure of nitrogen gas can be used and the reaction proceeds at room temperature. The procedure is very simple. A THF solution of TiCl4 or Ti(OiPr)4 (1 equiv.), Li (10 equiv.), and TMSCl (10 equiv.) was stirred under an atmosphere of nitrogen at room temperature overnight to give titanium–nitrogen complexes. Although the structures of the titanium–nitrogen complexes have not yet been determined, they would consist of N(TMS)3, X2TiN(TMS)2, and XTi=NTMS. Using this procedure, various heterocycles, such as indole, quinoline, pyrrole, pyrrolizine, and indolizine derivatives, could be synthesized from molecular nitrogen in good-to-moderate yields as a stoichiometric reaction based on a titanium complex by a one-pot reaction. Furthermore, monomorine I and pumiliotoxin C were synthesized from molecular nitrogen as a nitrogen source. This procedure was further extended for the syntheses of heterocycles using a catalytic amount of titanium complex; also, indole and pyrrole derivatives were obtained in high yields.

  过渡金属固氮是一个迷人的过程。我们之前已经报道过使用Yamamoto报道的钛-氮配合物将分子氮引入有机化合物的方法。我们开发了一种新的钛催化氮化过程，使用TiCl4在过量Li和TMSCl的存在下进行。在这种反应中，可以使用1大气压的氮气，反应在室温下进行。这个过程非常简单。将TiCl4或Ti(OiPr)4（1 equiv.）、Li（10 equiv.）和TMSCl（10 equiv.）的THF溶液在氮气气氛下在室温下搅拌过夜，得到钛-氮配合物。尽管钛-氮配合物的结构尚未确定，但它们可能由N(TMS)3、X2TiN(TMS)2和XTi=NTMS组成。使用这种方法，可以通过钛配合物作为定量反应的单锅反应，以良好至中等的收率合成各种杂环化合物，如吲哚、喹啉、吡咯、吡咯啉和吲哚啉衍生物。此外，使用分子氮作为氮源合成了monomorine I和pumiliotoxin C。这种方法进一步扩展，用于使用催化量的钛配合物合成杂环化合物；此外，以高收率获得了吲哚和吡咯衍生物。
• Propargyl Chlorides as Sources for Cobalt Stabilized .gamma.-Carbonyl Cations
  作者：C. Stephen Vizniowski、James R. Green、Tricia L. Breen、Andrea V. Dalacu

  DOI：10.1021/jo00128a022

  日期：1995.11

  Hexacarbonyldicobalt complexes of gamma-chloroalkynones and gamma-chloroalkynoates (5) were found to undergo silver-mediated Nicholas condensation reactions with silyl enol ethers or silyl ketene acetals (10) to give 1,6-dicarbonyl complexes 11 in fair to good yields. Substrates 5 with gamma-alkyl substitution formed diastereomeric products with enol silanes 10a and 10b. Reactions with propiophenone trimethylsilyl enol ether (10b) gave good levels of syn diastereoselection, whereas reactions with cyclohexanone trimethylsilyl enol ether (10a) were only slightly diastereoselective, favoring the anti diastereomer. When conducted in acetonitrile, the silver-mediated reaction of 5e gave a radical dimerization product 13, isolated as the syn diastereomer.