Methyl 7-(4-acetylphenyl)-3-oxohept-6-ynoate | 191329-62-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 7-(4-acetylphenyl)-3-oxohept-6-ynoate
• CAS: 191329-62-1
• 化学式: C₁₆H₁₆O₄
• 分子量: 272.301
• InChiKey: SRDTVTTWHLSPLS-UHFFFAOYSA-N

物化性质

• 沸点：
  424.4±35.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 7-(4-acetylphenyl)-3-oxohept-6-ynoate 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 以51%的产率得到Methyl 2-[5-[(4-acetylphenyl)methyl]furan-2-yl]acetate
  参考文献：
  名称：

  Synthesis of 2,5-Disubstituted Furans via Palladium-Catalyzed Annulation of Alkyl 3-Oxo-6-heptynoates

  摘要：

  The reaction of the readily available alkyl 3-oxo-6-heptynoates with aryl halides in the presence of K2CO3 and catalytic amounts of Pd(PPh3)(4) at 100 degrees C provides a valuable new route to 2,5-disubstituted furans 3. Most probably, the furan ring is generated through an annulation reaction promoted by sigma-arylpalladium complexes generated in situ and involving the nucleophilic attack of the ketonic oxygen across the carbon-carbon triple bond coordinated to palladium, followed by the base-catalyzed isomerization of the resultant stereoisomeric 2,5-dialkylidenetetrahydrofuran intermediates 4 and 5. The reaction is highly chemoselective. No evidence was obtained of carboannulation products. The reaction temperature has proven to be crucial for the success of the methodology. The K2CO3:alkyne ratio also affects the reaction outcome. The highest yields of furan derivatives have been obtained with aryl halides containing electron-withdrawing substituents, very likely because the higher acidity of the methylene protons of 4 and 5 favors the isomerization step. Extension of the methodology to methyl 3-oxo-7-substituted-6-heptynoates leads to the formation of 2,5-disubstituted furans containing a branched side chain. The presence of an alkyl substituent on the C-2 of the staring alkyne, however, seems to prevent the isomerization step. Treatment of ethyl 2-methyl-3-oxo-6-heptynoate under our standard conditions produced in fact the 2,5-dialkylidene derivative 5p in 42% yield, and no evidence of the corresponding furan derivative was attained.

  DOI：

  10.1021/jo962386v
• 作为产物：
  描述：

  炔丙基脲 在 4-二甲氨基吡啶 、 copper(l) iodide 、 bis(triphenylphosphine) palladium (Il) acetate 、 二乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 Methyl 7-(4-acetylphenyl)-3-oxohept-6-ynoate
  参考文献：
  名称：

  Synthesis of 2,5-Disubstituted Furans via Palladium-Catalyzed Annulation of Alkyl 3-Oxo-6-heptynoates

  摘要：

  The reaction of the readily available alkyl 3-oxo-6-heptynoates with aryl halides in the presence of K2CO3 and catalytic amounts of Pd(PPh3)(4) at 100 degrees C provides a valuable new route to 2,5-disubstituted furans 3. Most probably, the furan ring is generated through an annulation reaction promoted by sigma-arylpalladium complexes generated in situ and involving the nucleophilic attack of the ketonic oxygen across the carbon-carbon triple bond coordinated to palladium, followed by the base-catalyzed isomerization of the resultant stereoisomeric 2,5-dialkylidenetetrahydrofuran intermediates 4 and 5. The reaction is highly chemoselective. No evidence was obtained of carboannulation products. The reaction temperature has proven to be crucial for the success of the methodology. The K2CO3:alkyne ratio also affects the reaction outcome. The highest yields of furan derivatives have been obtained with aryl halides containing electron-withdrawing substituents, very likely because the higher acidity of the methylene protons of 4 and 5 favors the isomerization step. Extension of the methodology to methyl 3-oxo-7-substituted-6-heptynoates leads to the formation of 2,5-disubstituted furans containing a branched side chain. The presence of an alkyl substituent on the C-2 of the staring alkyne, however, seems to prevent the isomerization step. Treatment of ethyl 2-methyl-3-oxo-6-heptynoate under our standard conditions produced in fact the 2,5-dialkylidene derivative 5p in 42% yield, and no evidence of the corresponding furan derivative was attained.

  DOI：

  10.1021/jo962386v

文献信息

• Yb(OTf)3-Promoted ZnCl2-Catalyzed Conia-Ene Reaction of Linear β-Alkynic β-Dicarbonyls
  作者：Jin-Heng Li、Yu Liu、Ren-Jie Song

  DOI：10.1055/s-0030-1258213

  日期：2010.11

  An atom-economical and solvent-free ytterbium(III) triflate promoted, zinc(II) chloride catalyzed Conia-ene method has been developed for the construction of five- to six-membered-ring carbocycles. In the presence of zinc(II) chloride and ytterbium(III) triflate, a variety of linear β-alkynic β-keto esters and β-alkynic β-diketones were cyclized under neat conditions in moderate to good yields. It

  已经开发了一种原子经济且无溶剂的三氟甲磺酸（III）促进的氯化锌（II）催化的Conia-ene方法，用于构建五元至六元环的碳环。在氯化锌（II）和三氟甲磺酸（III）的存在下，在纯净条件下，以中等至良好的收率将各种线性的β-链烯基β-酮酸酯和β-链烯基β-二酮环化。值得注意的是，对五或六元环碳环的选择性取决于末端炔烃上的取代基。 氯化锌（II）-三氟甲磺酸（III）-Conia-ene反应-线性β-炔烃β-二羰基-碳环
• Copper/Silver-Cocatalyzed Conia-Ene Reaction of Linear β-Alkynic β<i>-</i>Ketoesters
  作者：Chen-Liang Deng、Ren-Jie Song、Sheng-Mei Guo、Zhi-Qiang Wang、Jin-Heng Li

  DOI：10.1021/ol7023289

  日期：2007.11.1

  A novel and general copper/silver catalytic system has been developed for the Conia-ene intramolecular reaction of linear beta-alkynic beta-ketoesters. In the presence of (CuOTf)(2)center dot C6H6 and AgSbF6 (or AgOAc), a variety of the linear 6-alkynic 6-ketoesters selectively underwent the Conia-ene intramolecular reaction in moderate to good yields.
• Synthesis of 2,5-Disubstituted Furans via Palladium-Catalyzed Annulation of Alkyl 3-Oxo-6-heptynoates
  作者：Sandro Cacchi、Giancarlo Fabrizi、Leonardo Moro

  DOI：10.1021/jo962386v

  日期：1997.8.1

  The reaction of the readily available alkyl 3-oxo-6-heptynoates with aryl halides in the presence of K2CO3 and catalytic amounts of Pd(PPh3)(4) at 100 degrees C provides a valuable new route to 2,5-disubstituted furans 3. Most probably, the furan ring is generated through an annulation reaction promoted by sigma-arylpalladium complexes generated in situ and involving the nucleophilic attack of the ketonic oxygen across the carbon-carbon triple bond coordinated to palladium, followed by the base-catalyzed isomerization of the resultant stereoisomeric 2,5-dialkylidenetetrahydrofuran intermediates 4 and 5. The reaction is highly chemoselective. No evidence was obtained of carboannulation products. The reaction temperature has proven to be crucial for the success of the methodology. The K2CO3:alkyne ratio also affects the reaction outcome. The highest yields of furan derivatives have been obtained with aryl halides containing electron-withdrawing substituents, very likely because the higher acidity of the methylene protons of 4 and 5 favors the isomerization step. Extension of the methodology to methyl 3-oxo-7-substituted-6-heptynoates leads to the formation of 2,5-disubstituted furans containing a branched side chain. The presence of an alkyl substituent on the C-2 of the staring alkyne, however, seems to prevent the isomerization step. Treatment of ethyl 2-methyl-3-oxo-6-heptynoate under our standard conditions produced in fact the 2,5-dialkylidene derivative 5p in 42% yield, and no evidence of the corresponding furan derivative was attained.