6-(2-butynyl)-8,8-dimethyl-1,4-dioxaspiro<4.4>nonane | 162977-97-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-(2-butynyl)-8,8-dimethyl-1,4-dioxaspiro<4.4>nonane
• 英文别名: 9-But-2-ynyl-7,7-dimethyl-1,4-dioxaspiro[4.4]nonane
• CAS: 162977-97-1
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: ORAXEZDMHBDLLG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二(三甲基硅氧基)环丁烯 、 6-(2-butynyl)-8,8-dimethyl-1,4-dioxaspiro<4.4>nonane 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以62%的产率得到4-acetyl-3,5,5a,6-tetrahydro-7,7-dimethycyclopentapentalen-1(2H)-one
  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
• 作为产物：
  描述：

  4,4-二甲基-2-氧代环戊烷羧酸甲酯 在 正丁基锂 、 potassium tert-butylate 、 水 、 对甲苯磺酸 、 lithium chloride 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 正己烷 、 二甲基亚砜 、 甲苯 、 叔丁醇 为溶剂， 反应 10.0h， 生成 6-(2-butynyl)-8,8-dimethyl-1,4-dioxaspiro<4.4>nonane
  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

• 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.