1-<2-<5-(Allyloxy)pent-1-ynyl>phenyl>-2-diazoethanone | 142458-68-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-<2-<5-(Allyloxy)pent-1-ynyl>phenyl>-2-diazoethanone
• 英文别名: o-<5-(allyloxy)-1-pentynyl>-α-diazoacetophenone；2-Diazo-1-[2-(5-prop-2-enoxypent-1-ynyl)phenyl]ethanone
• CAS: 142458-68-2
• 化学式: C₁₆H₁₆N₂O₂
• 分子量: 268.315
• InChiKey: VZAASZFUZPHGRZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  28.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-<2-<5-(Allyloxy)pent-1-ynyl>phenyl>-2-diazoethanone 在 Rh2[(+/-)-mandelate]4 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以81%的产率得到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
• 作为产物：
  描述：

  methyl o-<5-(allyloxy)-1-pentynyl>benzoate 在 potassium trimethylsilonate 作用下， 以 乙醚 为溶剂， 反应 7.0h， 生成 1-<2-<5-(Allyloxy)pent-1-ynyl>phenyl>-2-diazoethanone
  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：——