2-(2-propen-1-yl)-2-(1-oxo-1H-indenyl)-2,3,4,5-tetrahydrofuran | 142458-69-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 2-(2-propen-1-yl)-2-(1-oxo-1H-indenyl)-2,3,4,5-tetrahydrofuran
• 英文别名: 3-inden-1-one；3-(2-Allyl-tetrahydro-furan-2-yl)-inden-1-one；3-(2-prop-2-enyloxolan-2-yl)inden-1-one
• CAS: 142458-69-3
• 化学式: C₁₆H₁₆O₂
• 分子量: 240.302
• InChiKey: KQKAFDHYZHCGFH-UHFFFAOYSA-N

物化性质

• 沸点：
  375.7±42.0 °C(Predicted)
• 密度：
  1.159±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  methyl o-<5-(allyloxy)-1-pentynyl>benzoate 在 Rh2[(+/-)-mandelate]4 potassium trimethylsilonate 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 7.5h， 生成 2-(2-propen-1-yl)-2-(1-oxo-1H-indenyl)-2,3,4,5-tetrahydrofuran
  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

• Rhodium carbenoid mediated cyclizations of o-alkynyl-substituted .alpha.-diazoacetophenones
  作者：Albert Padwa、Keith E. Krumpe、Jamal M. Kassir

  DOI：10.1021/jo00044a032

  日期：1992.8

  o-Alkynyl-substituted alpha-diazoacetophenones undergo facile cyclization to indenone derivatives upon treatment with catalytic quantities of Rh(II) carboxylates. A variety of structural influences were encountered by varying the nature of the substituent group attached to the alkyne carbon atom. The cyclization reaction involves addition of a rhodium stabilized carbenoid onto the acetylenic pi-bond to generate a vinyl carbenoid. The vinyl carbenoid was found to undergo both CH and CC migration as well as delta-CH insertion into the alkyl backbone. Different catalysts were shown to result in significant variation in the product ratios for these reactions. Treatment of o-(5-(allyloxy)-1-pentynyl)-alpha-diazoacetophenone with rhodium(II) mandelate afforded 2-(2-propen-1-yl)-2-(1-oxo-1H-indenyl)-2,3,4,5-tetrahydrofuran in high yield. The formation of this compound involves initial formation of a vinyl carbenoid which reacts with the neighboring oxygen atom to give an oxonium ylide which subsequently undergoes a 2,3-sigmatropic rearrangement. When 2-ethynyl-alpha-diazoacetophenone is used, only products derived from 6-endo closure are observed. Substituted o-alkynyl alpha-diazoacetophenones give products derived from 5-exo cyclization. The mode of ring closure is controlled by both steric and electronic factors.
• Padwa Albert, Kassir Jamal M., Semones Mark A., Weingarten M. David, J. Org. Chem, 60 (1995) N 1, S 53-62
  作者：Padwa Albert, Kassir Jamal M., Semones Mark A., Weingarten M. David

  DOI：——

  日期：——
• A Tandem Cyclization-Onium Ylide Rearrangement-Cycloaddition Sequence for the Synthesis of Benzo-Substituted Cyclopentenones
  作者：Albert Padwa、Jamal M. Kassir、Mark A. Semones、M. David Weingarten

  DOI：10.1021/jo00106a014

  日期：1995.1

  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.