ethyl 2-allyl-6-methyl-3-oxo-6-heptenoate | 461663-55-8

• 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: ethyl 2-allyl-6-methyl-3-oxo-6-heptenoate
• CAS: 461663-55-8
• 化学式: C₁₃H₂₀O₃
• 分子量: 224.3
• InChiKey: PBYLANWKOHWDNW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.67
• 重原子数：
  16.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ethyl 2-allyl-6-methyl-3-oxo-6-heptenoate 在 bis[1,1-di(trifluoromethyl)ethoxy][(2,6-diisopropylphenyl)imino](2-methyl-2-phenylpropylidene)molybdenum 吡啶 、 咪唑 、 氢氧化钾 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 氯化亚砜 、 jones reagent 、 18-冠醚-6 、 (S)-(-)- α-甲基苄胺 、 potassium tert-butylate 、 sodium hydride 、 对甲苯磺酸 、 magnesium 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 苯 为溶剂， 反应 159.5h， 生成 (1S,7R)-8-acetyl-1,4-dimethylbicyclo[5.3.0]dec-3-ene
  参考文献：
  名称：

  Total Synthesis and Absolute Configuration of Liverwort Diterpenes, (−)-13(15)E,16E-3β,4β-Epoxy-18-hydroxysphenoloba-13(15),16-diene and (−)-13(15)Z,16E-3β,4β-Epoxy-18-hydroxysphenoloba-13(15),16-diene, by Use of the Ring Closing Metathesis Reaction Applied to Seven-Membered Carbocycles with a Trisubstituted Double Bond

  摘要：

  Seven-membered cyclic compounds possessing trisubstituted double bonds have been effectively constructed employing the Grubbs catalyst to effect olefin metathesis. The keto ester does not undergo cyclization; however, alcohols protected by the silyl groups smoothly cyclized into seven-membered compounds. The product was successfully converted to (-)-13(15)E,16E-3P,4P-epoxy18-hydroxysphenoloba-13(15),16-diene and (-)-13(15)Z,16E-3beta,4beta-epoxy-18-hydroxysphenoloba-13(15),16-diene, liverwort diterpenes isolated from Anastrophyllum auritum to establish the absolute configuration.

  DOI：

  10.1021/jo020287d
• 作为产物：
  描述：

  乙酰乙酸乙酯 、 alkaline earth salt of/the/ methylsulfuric acid 在 sodium ethanolate 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 25.0h， 生成 ethyl 2-allyl-6-methyl-3-oxo-6-heptenoate
  参考文献：
  名称：

  Total Synthesis and Absolute Configuration of Liverwort Diterpenes, (−)-13(15)E,16E-3β,4β-Epoxy-18-hydroxysphenoloba-13(15),16-diene and (−)-13(15)Z,16E-3β,4β-Epoxy-18-hydroxysphenoloba-13(15),16-diene, by Use of the Ring Closing Metathesis Reaction Applied to Seven-Membered Carbocycles with a Trisubstituted Double Bond

  摘要：

  Seven-membered cyclic compounds possessing trisubstituted double bonds have been effectively constructed employing the Grubbs catalyst to effect olefin metathesis. The keto ester does not undergo cyclization; however, alcohols protected by the silyl groups smoothly cyclized into seven-membered compounds. The product was successfully converted to (-)-13(15)E,16E-3P,4P-epoxy18-hydroxysphenoloba-13(15),16-diene and (-)-13(15)Z,16E-3beta,4beta-epoxy-18-hydroxysphenoloba-13(15),16-diene, liverwort diterpenes isolated from Anastrophyllum auritum to establish the absolute configuration.

  DOI：

  10.1021/jo020287d

文献信息

• Asymmetric induction in manganese(III)-based oxidative free-radical cyclizations of phenylmenthyl acetoacetates and 2,5-dimethylpyrrolidine acetoacetamides
  作者：Qingwei Zhang、Raju M. Mohan、Laura Cook、Sophia Kazanis、Daniel Peisach、Bruce M. Foxman、Barry B. Snider

  DOI：10.1021/jo00079a006

  日期：1993.12

  Mn(III)-based oxidative free-radical cyclization of phenylmenthyl ester 1e afforded 90% of 13 with 86% de. Cyclization of 31b provided 56% of (+)-podocarpic acid precursor 32e with 82% de. The direction of de was opposite in these two cases. Oxidative cyclization of a-methyl beta-keto ester 44b gave a 1:1.6 mixture of 46b and 47b while alpha-propyl beta-keto ester 44d produced a > 10:1 mixture of 46d and 47d indicating that the extent and direction of de is dependent on the size of the alpha-substituent The reaction proceeds through transition states 12 and 56 with large alpha-substituents and through transition states 19 and 57 with small a-substituents. The de depends on the double-bond substitution pattern as shown by the decreased de with 37b and 37d, and selectivity in the 5-exo cyclization of 64b, 65b, 70b, and 71b is low.