1,4-dimethyl-8-methylenebicyclo[3.2.1]octan-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,4-dimethyl-8-methylenebicyclo[3.2.1]octan-2-one
• 英文别名: (1S,4S,5S)-1,4-dimethyl-8-methylidenebicyclo[3.2.1]octan-2-one
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: YAXNPHBCCNHFOM-ARENWVFISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,4-dimethyl-8-methylenebicyclo[3.2.1]octan-2-one 以 甲苯 为溶剂， 反应 12.0h， 生成 (1S,2R,4S,5S)-2-{(S)-5-[(R)-3-(tert-Butyl-dimethyl-silanyloxy)-1-methyl-propyl]-2-methyl-cyclopent-1-enyl}-1,4-dimethyl-8-methylene-bicyclo[3.2.1]octan-2-ol
  参考文献：
  名称：

  Stereoselective Construction of the Dicyclopenta[a,d]cyclooctene Core of the Ceroplastin Sesterterpenes by Way of the Anionic Oxy-Cope Rearrangement

  摘要：

  Bicyclo[3.2.1]octanediones such as 9, which are readily available by double carbonylation of (1,3-cyclohexadiene)iron tricarbonyl complexes according to Eilbracht, are amenable to regiospecific methylenation under Wittig conditions. Reduction of 10 with copper hydride leads to 11, which can be resolved by application of Johnson's sulfoximine technology and oxidized to give the enantiopure antipodes of 10. Variously substituted cyclopentenyl anions undergo 1,2-addition to 10, providing carbinols which are capable of anionic oxy-Cope rearrangement via chair transition states. These structural reorganizations are fully stereocontrolled and lead directly to functionalized dicyclopenta[a,d]cyclooctenes. When 11 is treated analogously, only [1,3] sigmatropy is observed and inversion of stereochemistry at the migrating carbon prevails. Both processes exhibit impressive scaffolding powers and are characterized by brevity.

  DOI：

  10.1021/jo952165+
• 作为产物：
  描述：

  (1R,5S)-1,4-Dimethyl-bicyclo[3.2.1]oct-3-ene-2,8-dione 在 六甲基磷酰三胺 、 copper(l) iodide 、 正丁基锂 、 甲基锂 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 为溶剂， 反应 16.75h， 生成 1,4-dimethyl-8-methylenebicyclo[3.2.1]octan-2-one
  参考文献：
  名称：

  Stereoselective Construction of the Dicyclopenta[a,d]cyclooctene Core of the Ceroplastin Sesterterpenes by Way of the Anionic Oxy-Cope Rearrangement

  摘要：

  Bicyclo[3.2.1]octanediones such as 9, which are readily available by double carbonylation of (1,3-cyclohexadiene)iron tricarbonyl complexes according to Eilbracht, are amenable to regiospecific methylenation under Wittig conditions. Reduction of 10 with copper hydride leads to 11, which can be resolved by application of Johnson's sulfoximine technology and oxidized to give the enantiopure antipodes of 10. Variously substituted cyclopentenyl anions undergo 1,2-addition to 10, providing carbinols which are capable of anionic oxy-Cope rearrangement via chair transition states. These structural reorganizations are fully stereocontrolled and lead directly to functionalized dicyclopenta[a,d]cyclooctenes. When 11 is treated analogously, only [1,3] sigmatropy is observed and inversion of stereochemistry at the migrating carbon prevails. Both processes exhibit impressive scaffolding powers and are characterized by brevity.

  DOI：

  10.1021/jo952165+

文献信息

• Stereoselective Construction of the Dicyclopenta[<i>a,d</i>]cyclooctene Core of the Ceroplastin Sesterterpenes by Way of the Anionic Oxy-Cope Rearrangement
  作者：Leo A. Paquette、Shaowo Liang、Hui-Ling Wang

  DOI：10.1021/jo952165+

  日期：1996.1.1

  Bicyclo[3.2.1]octanediones such as 9, which are readily available by double carbonylation of (1,3-cyclohexadiene)iron tricarbonyl complexes according to Eilbracht, are amenable to regiospecific methylenation under Wittig conditions. Reduction of 10 with copper hydride leads to 11, which can be resolved by application of Johnson's sulfoximine technology and oxidized to give the enantiopure antipodes of 10. Variously substituted cyclopentenyl anions undergo 1,2-addition to 10, providing carbinols which are capable of anionic oxy-Cope rearrangement via chair transition states. These structural reorganizations are fully stereocontrolled and lead directly to functionalized dicyclopenta[a,d]cyclooctenes. When 11 is treated analogously, only [1,3] sigmatropy is observed and inversion of stereochemistry at the migrating carbon prevails. Both processes exhibit impressive scaffolding powers and are characterized by brevity.