4-(1-oxopentyl)-3,5,6,6a-tetrahydro-6a-((methoxycarbonyl)propyl)-1(2H)-pentalenone | 142421-73-6

• 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: 4-(1-oxopentyl)-3,5,6,6a-tetrahydro-6a-((methoxycarbonyl)propyl)-1(2H)-pentalenone
• 英文别名: Methyl 4-(3-oxo-6-pentanoyl-1,2,4,5-tetrahydropentalen-3a-yl)butanoate
• CAS: 142421-73-6
• 化学式: C₁₈H₂₆O₄
• 分子量: 306.402
• InChiKey: LKYNKQWJWWAQFW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  二(三甲基硅氧基)环丁烯 、 4-(2-Oct-3-ynyl-[1,3]dioxolan-2-yl)-butyric acid methyl ester 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以50%的产率得到4-(1-oxopentyl)-3,5,6,6a-tetrahydro-6a-((methoxycarbonyl)propyl)-1(2H)-pentalenone
  参考文献：
  名称：

  Ring-Enlarging Annulations. A One-Step Conversion of Cyclic Silyl Acyloins and .omega.-Alkynyl Acetals to Polycyclic Enediones

  摘要：

  new sequence of cationic reactions that converts cyclic silyl acyloins and omega-alkynyl acetals to polycyclic enediones is reported. For example, treatment of bis-1,2-((trimethylsilyl)oxy)cyclobutene and 2-(ethylenedioxy)-5-heptyne with excess boron trifluoride etherate in methylene chloride for 2 days provides 4-acetyl-3,5,6,6a-tetrahydro-6a-methyl-1-(2H)-pentalenone in 58% yield. This product is formed via a sequence involving a Mukaiyama aldol reaction, a pinacol ring expansion, and a 5-exo-dig alkynyl ketone cyclization. In the case of terminal alkynes, the last cyclization occurs in a 6-endo-dig fashion. The scope and limitations of this process are studied, and a number of bi- and tricyclic ring systems are formed.

  DOI：

  10.1021/jo00107a011

文献信息

• Annulative ring expansions. Direct conversion of .omega.-alkynyl acetals to polycyclic unsaturated ketones
  作者：Joseph Sisko、Aaron Balog、Dennis P. Curran

  DOI：10.1021/jo00042a007

  日期：1992.7

  Geminal acylation of omega-acetylenic acetals and bis(silyloxy)cycloalkenes under Lewis acid conditions preceded cationic cyclization of the alkyne onto the ketone to produce polycyclic unsaturated ketones.
• Ring-Enlarging Annulations. A One-Step Conversion of Cyclic Silyl Acyloins and .omega.-Alkynyl Acetals to Polycyclic Enediones
  作者：Aaron Balog、Dennis P. Curran

  DOI：10.1021/jo00107a011

  日期：1995.1

  new sequence of cationic reactions that converts cyclic silyl acyloins and omega-alkynyl acetals to polycyclic enediones is reported. For example, treatment of bis-1,2-((trimethylsilyl)oxy)cyclobutene and 2-(ethylenedioxy)-5-heptyne with excess boron trifluoride etherate in methylene chloride for 2 days provides 4-acetyl-3,5,6,6a-tetrahydro-6a-methyl-1-(2H)-pentalenone in 58% yield. This product is formed via a sequence involving a Mukaiyama aldol reaction, a pinacol ring expansion, and a 5-exo-dig alkynyl ketone cyclization. In the case of terminal alkynes, the last cyclization occurs in a 6-endo-dig fashion. The scope and limitations of this process are studied, and a number of bi- and tricyclic ring systems are formed.