Spirooctan>-3'-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: Spirooctan>-3'-one
• 英文别名: Spiro[cyclopentane-1,6'-2'-(methoxycarbonyl)-5'-methyl-8'-oxabicyclo[3.2.1]octan]-3'-one；methyl (1S,5S)-5-methyl-3-oxospiro[8-oxabicyclo[3.2.1]octane-6,1'-cyclopentane]-2-carboxylate
• 化学式: C₁₄H₂₀O₄
• 分子量: 252.31
• InChiKey: VTNNGIWAVMSQPQ-BJEKPXQXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1,3-bis(trimethylsiloxy)-1-methoxybuta-1,3-diene 、 1-Acetyl-1-(2-oxoethyl)cyclopentane 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以76%的产率得到Spirooctan>-3'-one
  参考文献：
  名称：

  Neighboring group participation in Lewis acid-promoted [3 + 4] and [3 + 5] annulations. The stereocontrolled synthesis of tricyclic ethers

  摘要：

  A variety of 1,4- and 1,5-keto aldehydes derived from cycloalkanes are coupled with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of either TMSOTf or TrSbCl6 to generate tricyclic ethers. The reactions proceed with excellent regiochemical control by a mechanism involving neighboring group participation. This mechanism involves initial formation of a bicyclic oxocarbenium ion intermediate from the keto aldehyde substrates. The geometries of selected bicyclic intermediates have been optimized using the AM1 method allowing successful prediction of the stereochemical outcomes in the cyclization in most cases. Epimerization of alpha-chiral keto aldehyde substrates does not appear to occur in these Lewis acid-promoted annulation reactions.

  DOI：

  10.1021/jo00074a018

文献信息

• Neighboring group participation in Lewis acid-promoted [3 + 4] and [3 + 5] annulations. The stereocontrolled synthesis of tricyclic ethers
  作者：Gary A. Molander、Kimberly O. Cameron

  DOI：10.1021/jo00074a018

  日期：1993.10

  A variety of 1,4- and 1,5-keto aldehydes derived from cycloalkanes are coupled with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of either TMSOTf or TrSbCl6 to generate tricyclic ethers. The reactions proceed with excellent regiochemical control by a mechanism involving neighboring group participation. This mechanism involves initial formation of a bicyclic oxocarbenium ion intermediate from the keto aldehyde substrates. The geometries of selected bicyclic intermediates have been optimized using the AM1 method allowing successful prediction of the stereochemical outcomes in the cyclization in most cases. Epimerization of alpha-chiral keto aldehyde substrates does not appear to occur in these Lewis acid-promoted annulation reactions.