2-(N-benzoylprop-2-ynylamino)-2-benzylpenta-3,4-dienoic acid methyl ester | 734547-75-2

• 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: 2-(N-benzoylprop-2-ynylamino)-2-benzylpenta-3,4-dienoic acid methyl ester
• 英文别名: 2-(benzoyl(prop-2-ynyl)amino)-2-benzylhexa-3,4-dienoic acid methyl ester
• CAS: 734547-75-2
• 化学式: C₂₃H₂₁NO₃
• 分子量: 359.425
• InChiKey: UOFVIUGXSLTIQS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(N-benzoylprop-2-ynylamino)-2-benzylpenta-3,4-dienoic acid methyl ester 在 palladium on activated charcoal 4 A molecular sieve 、 氢气 、 3-苄基羟乙基甲基噻唑氯化锂 、 溶剂黄146 、 三乙胺 作用下， 以 1,4-二氧六环 、 甲醇 、 二甲基亚砜 、 甲苯 为溶剂， 20.0~90.0 ℃ 、101.33 kPa 条件下， 反应 14.33h， 生成 5-benzoyl-1,4-dibenzyl-2-propyl-3b,4,5,6,6a,7-hexahydro-1H-1,5-diazacyclopenta[a]pentalene-1-carboxylic acid methyl ester
  参考文献：
  名称：

  Heterocyclic α-Alkylidene Cyclopentenones Obtained via a Pauson−Khand Reaction of Amino Acid Derived Allenynes. A Scope and Limitation Study Directed toward the Preparation of a Tricyclic Pyrrole Library

  摘要：

  [GRAPHICS]The synthesis of a novel class of tricyclic pyrroles has been accomplished by using a Pauson-Khand/Stetter/Paal-Knorr reaction sequence. Full details of the Pauson-Khand reaction of amino acid tethered allenynes 4a-e and 9a-d are disclosed. The study of this reaction led to the discovery of an unprecedented substituent effect on the diastereoselectivity of the MO(CO)(6) mediated allenic Pauson-Khand reaction. It was found that amino acid tethered allenynes with aromatic side chains afford alpha-alkylidene cyclopentenones with the opposite diastereoselectivity compared to those with aliphatic side chains. This effect has been attributed to complexation of the metal mediator to the aromatic ring in the substrate. Furthermore, an isomerization of one of the diastereomers of the a-alkylidene cyclopentenones was encountered, leading to eventual decomposition. The stable diastereomers were found to react well in the Stetter reaction leading to 1,4-diketones that were converted to pyrroles. The observation that the first generation of 2-alkyl-substituted pyrroles was unstable led to a second generation of 2-carboxamide pyrroles with sufficient stability for biological tests which are in progress.

  DOI：

  10.1021/jo0481607
• 作为产物：
  描述：

  2-benzoylamino-2-benzylpenta-3,4-dienoic acid methyl ester 、 3-溴丙炔 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 以66%的产率得到2-(N-benzoylprop-2-ynylamino)-2-benzylpenta-3,4-dienoic acid methyl ester
  参考文献：
  名称：

  Allenes and Transition Metals:  A Diverging Approach to Heterocycles

  摘要：

  [GRAPHICS]An alkynyl allene has been converted to heterocycles possessing an alpha-alkylidene cyclopentenone, a 4-alkylidene cyclopentenone, or a cross-conjugated triene. Thus, a common intermediate has been converted to three structurally unique compounds by changing only the reaction conditions and, therefore, controlling various reaction pathways.

  DOI：

  10.1021/ol0492391

文献信息

• Heterocyclic α-Alkylidene Cyclopentenones Obtained via a Pauson−Khand Reaction of Amino Acid Derived Allenynes. A Scope and Limitation Study Directed toward the Preparation of a Tricyclic Pyrrole Library
  作者：Kay M. Brummond、Dennis P. Curran、Branko Mitasev、Stefan Fischer

  DOI：10.1021/jo0481607

  日期：2005.3.1

  [GRAPHICS]The synthesis of a novel class of tricyclic pyrroles has been accomplished by using a Pauson-Khand/Stetter/Paal-Knorr reaction sequence. Full details of the Pauson-Khand reaction of amino acid tethered allenynes 4a-e and 9a-d are disclosed. The study of this reaction led to the discovery of an unprecedented substituent effect on the diastereoselectivity of the MO(CO)(6) mediated allenic Pauson-Khand reaction. It was found that amino acid tethered allenynes with aromatic side chains afford alpha-alkylidene cyclopentenones with the opposite diastereoselectivity compared to those with aliphatic side chains. This effect has been attributed to complexation of the metal mediator to the aromatic ring in the substrate. Furthermore, an isomerization of one of the diastereomers of the a-alkylidene cyclopentenones was encountered, leading to eventual decomposition. The stable diastereomers were found to react well in the Stetter reaction leading to 1,4-diketones that were converted to pyrroles. The observation that the first generation of 2-alkyl-substituted pyrroles was unstable led to a second generation of 2-carboxamide pyrroles with sufficient stability for biological tests which are in progress.
• Allenes and Transition Metals:  A Diverging Approach to Heterocycles
  作者：Kay M. Brummond、Branko Mitasev

  DOI：10.1021/ol0492391

  日期：2004.6.1

  [GRAPHICS]An alkynyl allene has been converted to heterocycles possessing an alpha-alkylidene cyclopentenone, a 4-alkylidene cyclopentenone, or a cross-conjugated triene. Thus, a common intermediate has been converted to three structurally unique compounds by changing only the reaction conditions and, therefore, controlling various reaction pathways.