bicyclo<2.2.2>octane-cis-2,3-diyl carbonate | 173778-81-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: bicyclo<2.2.2>octane-cis-2,3-diyl carbonate
• 英文别名: (2R,6S)-3,5-dioxatricyclo[5.2.2.02,6]undecan-4-one
• CAS: 173778-81-9
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: PENVRVLZFGZXNB-HYNHDVCUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bicyclo<2.2.2>octane-cis-2,3-diyl carbonate 在 sodium hydroxide 、 二甲基亚砜 、 三乙胺 、 三氟乙酸酐 作用下， 反应 7.0h， 生成 双环[2.2.2]辛烷-2,3-二酮
  参考文献：
  名称：

  Transition Metal Mediated Exo Selective Diels−Alder Reactions:  Preparation of 2-Cobalt-Substituted 1,3-Dienes Containing C₂ Symmetric 2,3-Dibenzobicyclo[2.2.2]octanedione Dioxime Equatorial Ligands and Their Use in Thermal and Lewis Acid Catalyzed 4 + 2 Cycloadditions

  摘要：

  The preparation of C-2 symmetric 2,3-dibenzobicyclo[2.2.2]octanedione dioxime is reported. This ligand is then used in the preparation of a (pyridine)(glyoxime)(2)cobalt(III) chloride complex. The chloride is reduced to a cobaloxime anion which reacted with allenic electrophiles to produce (pyridine)(glyoxime)(2)cobalt-1,3-dienyl complexes. Thermal and Lewis acid catalyzed Diels-Alder reactions of these dienyl complexes as well as the complexes with glyoxime = diphenylglyoxime and dimethylglyoxime are reported. In most cases these Diels-Alder reactions are anti (exo) selective, and in many cases diastereoselectivities are >20:1. Cycloadduct demetalation reactions are also reported which preserve cycloaddition stereochemistry and provide cobalt complexes which can be recycled into the starting dienyl complex.

  DOI：

  10.1021/jo951505o
• 作为产物：
  描述：

  在 platinum(IV) oxide 氢气 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以97.8%的产率得到bicyclo<2.2.2>octane-cis-2,3-diyl carbonate
  参考文献：
  名称：

  Transition Metal Mediated Exo Selective Diels−Alder Reactions:  Preparation of 2-Cobalt-Substituted 1,3-Dienes Containing C₂ Symmetric 2,3-Dibenzobicyclo[2.2.2]octanedione Dioxime Equatorial Ligands and Their Use in Thermal and Lewis Acid Catalyzed 4 + 2 Cycloadditions

  摘要：

  The preparation of C-2 symmetric 2,3-dibenzobicyclo[2.2.2]octanedione dioxime is reported. This ligand is then used in the preparation of a (pyridine)(glyoxime)(2)cobalt(III) chloride complex. The chloride is reduced to a cobaloxime anion which reacted with allenic electrophiles to produce (pyridine)(glyoxime)(2)cobalt-1,3-dienyl complexes. Thermal and Lewis acid catalyzed Diels-Alder reactions of these dienyl complexes as well as the complexes with glyoxime = diphenylglyoxime and dimethylglyoxime are reported. In most cases these Diels-Alder reactions are anti (exo) selective, and in many cases diastereoselectivities are >20:1. Cycloadduct demetalation reactions are also reported which preserve cycloaddition stereochemistry and provide cobalt complexes which can be recycled into the starting dienyl complex.

  DOI：

  10.1021/jo951505o

文献信息

• Transition Metal Mediated <i>Exo </i>Selective Diels−Alder Reactions:  Preparation of 2-Cobalt-Substituted 1,3-Dienes Containing <i>C</i>₂ Symmetric 2,3-Dibenzobicyclo[2.2.2]octanedione Dioxime Equatorial Ligands and Their Use in Thermal and Lewis Acid Catalyzed 4 + 2 Cycloadditions
  作者：Marcus W. Wright、Mark E. Welker

  DOI：10.1021/jo951505o

  日期：1996.1.1

  The preparation of C-2 symmetric 2,3-dibenzobicyclo[2.2.2]octanedione dioxime is reported. This ligand is then used in the preparation of a (pyridine)(glyoxime)(2)cobalt(III) chloride complex. The chloride is reduced to a cobaloxime anion which reacted with allenic electrophiles to produce (pyridine)(glyoxime)(2)cobalt-1,3-dienyl complexes. Thermal and Lewis acid catalyzed Diels-Alder reactions of these dienyl complexes as well as the complexes with glyoxime = diphenylglyoxime and dimethylglyoxime are reported. In most cases these Diels-Alder reactions are anti (exo) selective, and in many cases diastereoselectivities are >20:1. Cycloadduct demetalation reactions are also reported which preserve cycloaddition stereochemistry and provide cobalt complexes which can be recycled into the starting dienyl complex.