(Z)-3-(1-hexenyl)inden-1-one | 142458-67-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: (Z)-3-(1-hexenyl)inden-1-one
• 英文别名: 3-[(Z)-hex-1-enyl]inden-1-one
• CAS: 142458-67-1
• 化学式: C₁₅H₁₆O
• 分子量: 212.291
• InChiKey: KIJWGRFNRRAYJX-YVMONPNESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-(1-heptynyl)-α-diazoacetophenone 在 Rh2[(+/-)-mandelate]4 作用下， 以 氯仿 为溶剂， 反应 0.5h， 生成 (Z)-3-(1-hexenyl)inden-1-one 、 3-(2-methyl-1-cyclopentyl)inden-1-one 、 3-(2-methyl-1-cyclopentyl)inden-1-one
  参考文献：
  名称：

  Rhodium carbenoid mediated cyclizations of o-alkynyl-substituted .alpha.-diazoacetophenones

  摘要：

  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.

  DOI：

  10.1021/jo00044a032

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.