7,9,9-Trimethylspiro[4.5]dec-6-ene-1,4-dione

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7,9,9-Trimethylspiro[4.5]dec-6-ene-1,4-dione
• 英文别名: 7,7,9-Trimethylspiro[4.5]dec-9-ene-1,4-dione
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: QOMCYVMLBLUNGW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7,9,9-Trimethylspiro[4.5]dec-6-ene-1,4-dione 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以69%的产率得到(4R*,5S*)-4-hydroxy-7,9,9-trimethylspiro[4.5]dec-6-en-1-one
  参考文献：
  名称：

  包含螺[4.4]壬烷亚单元的三环化合物的组装

  摘要：

  通过路易斯酸催化的 1,2-双（（三甲基甲硅烷基）氧基）环丁烯 5 的反应，衍生自不饱和环己烯酮衍生物的缩酮的螺环化导致螺 [4.5] 癸烯二酮 9 和 30。这些转化为螺 [4.4]壬烯衍生物 25 和 35/36 通过类似的序列包括臭氧分解和羟醛环重闭合。环状双键的还原使得第三个环也可以通过羟醛反应轻松闭合。这项工作导致了来自 9 的单一氧化角三喹烷 28，以及来自 30 的三环 [6.2.1.01,5] 十一烷衍生物 41。还从 9 中获得了氧杂三环 [5.3.1.01,5] 十一烷衍生物 19。 关键词：螺环化、成对酰化、倍半萜烯合成。

  DOI：

  10.1139/v97-080
• 作为产物：
  描述：

  异佛尔酮 、 二(三甲基硅氧基)环丁烯 在 三氟化硼乙醚 作用下， 反应 65.0h， 以33%的产率得到7,9,9-Trimethylspiro[4.5]dec-6-ene-1,4-dione
  参考文献：
  名称：

  Lewis Acid Catalyzed Geminal Acylation Reaction of Ketones with 1,2-Bis[(trimethylsilyl)oxy]cyclobutene: Direct Formation of 2,2-Disubstituted 1,3-Cyclopentanediones

  摘要：

  Ketones reacted with 1,2-bis((trimethylsilyl)oxy)cyclobutene (1) under catalysis by boron trifluoride etherate to yield 2,2-disubstituted 1,3-cyclopentanedione products via silylated cyclobutanone intermediates in a two-step, one-pot process. In many instances addition of a small amount of water to the reaction medium after completion of the first step assisted the subsequent rearrangement to the product, such that reversion of the intermediate to the starting ketone became an insignificant process. Yields were best with cyclohexanones (>90%), but steric hindrance and conjugated double bonds reduced yields considerably.

  DOI：

  10.1021/jo00085a041

文献信息

• Lewis Acid Catalyzed Geminal Acylation Reaction of Ketones with 1,2-Bis[(trimethylsilyl)oxy]cyclobutene: Direct Formation of 2,2-Disubstituted 1,3-Cyclopentanediones
  作者：Tracy J. Jenkins、D. Jean Burnell

  DOI：10.1021/jo00085a041

  日期：1994.3

  Ketones reacted with 1,2-bis((trimethylsilyl)oxy)cyclobutene (1) under catalysis by boron trifluoride etherate to yield 2,2-disubstituted 1,3-cyclopentanedione products via silylated cyclobutanone intermediates in a two-step, one-pot process. In many instances addition of a small amount of water to the reaction medium after completion of the first step assisted the subsequent rearrangement to the product, such that reversion of the intermediate to the starting ketone became an insignificant process. Yields were best with cyclohexanones (>90%), but steric hindrance and conjugated double bonds reduced yields considerably.
• Assembly of tricyclic compounds that include the spiro[4.4]nonane subunit
  作者：Pei-Ying Liu、Yong-Jin Wu、D. Jean Burnell

  DOI：10.1139/v97-080

  日期：1997.6.1

  Spiroannulation of ketals derived from unsaturated cyclohexenone derivatives by the Lewis acid-catalyzed reaction of 1,2-bis((trimethylsilyl)oxy)cyclobutene 5 led to spiro[4.5]decene-diones 9 and 30. These were transformed into spiro[4.4]nonene derivatives 25 and 35/36 via similar sequences involving ozonolysis and aldol ring reclosure. Reduction of an annular double bond allowed facile closure of a third ring

  通过路易斯酸催化的 1,2-双（（三甲基甲硅烷基）氧基）环丁烯 5 的反应，衍生自不饱和环己烯酮衍生物的缩酮的螺环化导致螺 [4.5] 癸烯二酮 9 和 30。这些转化为螺 [4.4]壬烯衍生物 25 和 35/36 通过类似的序列包括臭氧分解和羟醛环重闭合。环状双键的还原使得第三个环也可以通过羟醛反应轻松闭合。这项工作导致了来自 9 的单一氧化角三喹烷 28，以及来自 30 的三环 [6.2.1.01,5] 十一烷衍生物 41。还从 9 中获得了氧杂三环 [5.3.1.01,5] 十一烷衍生物 19。 关键词：螺环化、成对酰化、倍半萜烯合成。