1-Methyl-4-(2-methyl-3-oxo-3H-inden-1-yl)-7-oxabicyclo<2.2.1>hept-2-ene-2,3 dicarboxylic acid dimethyl ester | 153563-32-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 1-Methyl-4-(2-methyl-3-oxo-3H-inden-1-yl)-7-oxabicyclo<2.2.1>hept-2-ene-2,3 dicarboxylic acid dimethyl ester
• 英文别名: Dimethyl 1-methyl-4-(2-methyl-1-oxo-1H-inden-3-yl)-7-oxabicyclo[2.2.1]hept-2-ene-2,3-dicarboxylate；dimethyl 1-methyl-4-(2-methyl-3-oxoinden-1-yl)-7-oxabicyclo[2.2.1]hept-2-ene-2,3-dicarboxylate
• CAS: 153563-32-7
• 化学式: C₂₁H₂₀O₆
• 分子量: 368.386
• InChiKey: JAYRJXXDWWDZEB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-Methyl-4-(2-methyl-3-oxo-3H-inden-1-yl)-7-oxabicyclo<2.2.1>hept-2-ene-2,3 dicarboxylic acid dimethyl ester 在 吡啶 、 magnesium 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 13.0h， 生成 (Z)-Methyl 2-<5-(methoxyimino)dec-9-en-1-ynyl>benzoate
  参考文献：
  名称：

  A Tandem Cyclization-Onium Ylide Rearrangement-Cycloaddition Sequence for the Synthesis of Benzo-Substituted Cyclopentenones

  摘要：

  A new annulation sequence leading to benzo-substituted cyclopentenones is effected by treating o-alkynyl-substituted alpha-diazoacetophenones containing tethered heteroatoms with Rh(II) carboxylates. The reaction involves addition of the initially formed keto carbenoid onto the acetylenic pi-bond to give a rearranged vinyl carbenoid. Sulfonium ylide formation occurred both intra- and intermolecularly when the reaction was carried out in the presence of a sulfide. In the case where an ether oxygen was present on the backbone of the vinyl carbenoid, the resulting oxonium ylide underwent a [1,2]- or [2,3]-shift to give the rearranged product. These cyclic metallocarbenoids were also found to interact with a neighboring carbonyl or oximino pi-bond to produce carbonyl or azomethine ylides. The 1,3-dipoles generated in this manner were trapped with dimethyl acetylenedicarboxylate. The domino transformation was also performed intramolecularly by attaching a trapping agent directly to the carbonyl group. Incorporation of an amido carbonyl on the alkyne side chain was found to dramatically alter the course of the tandem annulation reaction. A novel rearranged cycloadduct was formed in high yield whose structure was elucidated by X-ray crystallography. The mechanism for its formation involves the opening of a transient intermediate oxabicyclo[2.2.1]heptane followed by a Wagner-Meerwein rearrangement.

  DOI：

  10.1021/jo00106a014
• 作为产物：
  描述：

  2-(but-3'-ynyl)-2-methyl-1,3-dioxolane 在 rhodium(II) acetate dimer 、 trans-bis(triphenylphosphine)palladium(II) chloride copper(l) iodide 、 potassium trimethylsilonate 、 水 、 4-甲基苯磺酸吡啶 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 丙酮 为溶剂， 反应 62.25h， 生成 1-Methyl-4-(2-methyl-3-oxo-3H-inden-1-yl)-7-oxabicyclo<2.2.1>hept-2-ene-2,3 dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  A Tandem Cyclization-Onium Ylide Rearrangement-Cycloaddition Sequence for the Synthesis of Benzo-Substituted Cyclopentenones

  摘要：

  A new annulation sequence leading to benzo-substituted cyclopentenones is effected by treating o-alkynyl-substituted alpha-diazoacetophenones containing tethered heteroatoms with Rh(II) carboxylates. The reaction involves addition of the initially formed keto carbenoid onto the acetylenic pi-bond to give a rearranged vinyl carbenoid. Sulfonium ylide formation occurred both intra- and intermolecularly when the reaction was carried out in the presence of a sulfide. In the case where an ether oxygen was present on the backbone of the vinyl carbenoid, the resulting oxonium ylide underwent a [1,2]- or [2,3]-shift to give the rearranged product. These cyclic metallocarbenoids were also found to interact with a neighboring carbonyl or oximino pi-bond to produce carbonyl or azomethine ylides. The 1,3-dipoles generated in this manner were trapped with dimethyl acetylenedicarboxylate. The domino transformation was also performed intramolecularly by attaching a trapping agent directly to the carbonyl group. Incorporation of an amido carbonyl on the alkyne side chain was found to dramatically alter the course of the tandem annulation reaction. A novel rearranged cycloadduct was formed in high yield whose structure was elucidated by X-ray crystallography. The mechanism for its formation involves the opening of a transient intermediate oxabicyclo[2.2.1]heptane followed by a Wagner-Meerwein rearrangement.

  DOI：

  10.1021/jo00106a014

文献信息

• Synthesis of oxa-bicyclic ring systems via a tandem Rh(II) catalyzed cyclization-cycloaddition sequence
  作者：Albert Padwa、Jamal M. Kassir、Mark A. Semones、M.David Weingarten

  DOI：10.1016/s0040-4039(00)61493-4

  日期：1993.12

  A new annulation sequence leading to oxabicyclic ring systems is effected by treating o-alkynyl substituted alpha-diazoacetophenones containing tethered carbonyl groups with Rh(II) carboxylates in the presence of C-C pi-bonds.