2-(methoxycarbonyl)-5-phenylpent-4-ynoic acid | 1374404-32-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-(methoxycarbonyl)-5-phenylpent-4-ynoic acid
• 英文别名: 2-Methoxycarbonyl-5-phenylpent-4-ynoic acid；2-methoxycarbonyl-5-phenylpent-4-ynoic acid
• CAS: 1374404-32-6
• 化学式: C₁₃H₁₂O₄
• 分子量: 232.236
• InChiKey: MNUDAELVEWHXKC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  ——	dimethyl 2-(3-phenylprop-2-yn-1-yl)malonate	346621-58-7	C14H14O4	246.263
  炔丙基丙二酸二甲酯	dimethyl (prop-2-yn-1-yl)malonate	95124-07-5	C8H10O4	170.165

反应信息

• 作为反应物：
  描述：

  2-(methoxycarbonyl)-5-phenylpent-4-ynoic acid 在 C₁₂H₁₅AuCl₃N₃O₃S 、 水 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以28%的产率得到5-benzylidene-2-oxotetrahydrofuran-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Cycloisomerization versus Hydration Reactions in Aqueous Media: A Au(III)-NHC Catalyst That Makes the Difference

  摘要：

  A novel water-soluble Au(III)-NHC complex has been synthesized and successfully applied in the intramolecular cyclization of gamma-alkynoic acids into enol-lactones under biphasic toluene/water conditions, thus representing a rare example of an active and selective catalyst for this transformation In aqueous media. Remarkably, competing alkyne hydration processes were not observed, even during the desymmetrization reaction of challenging 1,6-diyne substrates. In addition, after phase separation, the water-soluble Au(III) catalyst could be recycled 10 times without loss of activity or selectivity.

  DOI：

  10.1021/ol300811e
• 作为产物：
  描述：

  炔丙基丙二酸二甲酯 在 双(乙腈)氯化钯(II) 、 copper(l) iodide 、 三乙胺 、 三苯基膦 、 potassium hydroxide 作用下， 以 甲醇 为溶剂， 反应 37.0h， 生成 2-(methoxycarbonyl)-5-phenylpent-4-ynoic acid
  参考文献：
  名称：

  咪唑并[1,5-a]吡啶-3-亚烷基用作金属-咪唑协同催化的平台：炔烃系羧酸的银催化环化

  摘要：

  具有5-（4- （叔丁基）-1 H-咪唑-1-基）-咪唑的银络合物[1,5- a]吡啶-3-亚烷基配体被合成为金属咪唑酸碱协同催化剂。单晶XRD分析表明银原子位于咪唑环附近，并且阳离子银络合物通过银金属和咪唑侧基之间的配位形成二聚体。这些阳离子银络合物可作为炔烃系羧酸环化的催化剂。NMR实验表明，二咪唑阳离子银配合物在咪唑部分质子化时解离为单体，从而导致乙腈与银原子的配位。DFT计算结果支持了咪唑银的酸碱协同作用，从而有效地进行了炔-羧酸环化反应。

  DOI：

  10.1002/adsc.202001515

文献信息

• Gold(I)-Catalysed Cyclisation of Alkynoic Acids: Towards an Efficient and Eco-Friendly Synthesis of γ-, δ- and ϵ-Lactones
  作者：Danila Gasperini、Lorenzo Maggi、Stéphanie Dupuy、Richard M. P. Veenboer、David B. Cordes、Alexandra M. Z. Slawin、Steven P. Nolan

  DOI：10.1002/adsc.201600575

  日期：2016.12.7

  The improved synthesis of γ‐, δ‐ and ϵ‐lactones using a dinuclear N‐heterocyclic carbene (NHC)‐gold(I) catalyst is reported. This solvent‐free process provides access to γ‐ and δ‐lactones in high regio‐ and stereoselectivity. Reactions were performed at low catalyst loadings and without the need for any additives. The use of a digold pre‐catalyst provides a new synthetic route to functionalised ϵ‐lactones

  据报道，使用双核N-杂环卡宾（NHC）-金（I）催化剂可改善γ-，δ-和γ-内酯的合成。这种无溶剂的方法可以以较高的区域和立体选择性获得γ和δ内酯。反应在低催化剂负载下进行，不需要任何添加剂。使用digold预催化剂为功能化的β-内酯提供了一条新的合成途径，而使用以前的方法很难获得。
• Cycloisomerization versus Hydration Reactions in Aqueous Media: A Au(III)-NHC Catalyst That Makes the Difference
  作者：Eder Tomás-Mendivil、Patrick Y. Toullec、Josefina Díez、Salvador Conejero、Véronique Michelet、Victorio Cadierno

  DOI：10.1021/ol300811e

  日期：2012.5.18

  A novel water-soluble Au(III)-NHC complex has been synthesized and successfully applied in the intramolecular cyclization of gamma-alkynoic acids into enol-lactones under biphasic toluene/water conditions, thus representing a rare example of an active and selective catalyst for this transformation In aqueous media. Remarkably, competing alkyne hydration processes were not observed, even during the desymmetrization reaction of challenging 1,6-diyne substrates. In addition, after phase separation, the water-soluble Au(III) catalyst could be recycled 10 times without loss of activity or selectivity.
• Use of Imidazo[1,5‐ <i>a</i> ]pyridin‐3‐ylidene as a Platform for Metal‐Imidazole Cooperative Catalysis: Silver‐Catalyzed Cyclization of Alkyne‐Tethered Carboxylic Acids
  作者：Vishal Kumar Rawat、Kosuke Higashida、Masaya Sawamura

  DOI：10.1002/adsc.202001515

  日期：2021.3.16

  Silver complexes with 5‐(4‐(tert‐butyl)‐1H‐imidazol‐1‐yl)‐imidazo[1,5‐a]pyridin‐3‐ylidene ligands were synthesized as metal‐imidazole acid‐base cooperative catalysts. Single crystal XRD analysis revealed that the silver atom was located in the vicinity of the imidazole ring and that cationic silver complexes formed dimers through coordination between the silver metal and the imidazole pendant. These

  具有5-（4- （叔丁基）-1 H-咪唑-1-基）-咪唑的银络合物[1,5- a]吡啶-3-亚烷基配体被合成为金属咪唑酸碱协同催化剂。单晶XRD分析表明银原子位于咪唑环附近，并且阳离子银络合物通过银金属和咪唑侧基之间的配位形成二聚体。这些阳离子银络合物可作为炔烃系羧酸环化的催化剂。NMR实验表明，二咪唑阳离子银配合物在咪唑部分质子化时解离为单体，从而导致乙腈与银原子的配位。DFT计算结果支持了咪唑银的酸碱协同作用，从而有效地进行了炔-羧酸环化反应。