2-(2-oxoethyl)-2-(3-phenylprop-2-ynyl)malonic acid diethyl ester | 207685-01-6

• 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-(2-oxoethyl)-2-(3-phenylprop-2-ynyl)malonic acid diethyl ester
• 英文别名: Diethyl 2-(2-oxoethyl)-2-(3-phenylprop-2-ynyl)propanedioate
• CAS: 207685-01-6
• 化学式: C₁₈H₂₀O₅
• 分子量: 316.354
• InChiKey: QWEPPHDUFJMAPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-(2-oxoethyl)-2-(3-phenylprop-2-ynyl)malonic acid diethyl ester 在 silver hexafluoroantimonate 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 为溶剂， 以74%的产率得到3-benzoylcyclopent-3-ene-1,1-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Alkynes as Synthetic Equivalents to Stabilized Wittig Reagents:  Intra- and Intermolecular Carbonyl Olefinations Catalyzed by Ag(I), BF₃, and HBF₄

  摘要：

  The first use of cationic silver (AgSbF4) as a catalyst for intra- and intermolecular alkyne-carbonyl coupling to form conjugated enones is described, and a comparison to corresponding Bronsted acid (HBF4) and Lewis acid (BF3) catalyst systems is made. Notably, intermolecular coupling proceeds stereoselectively to afford the corresponding trisubstituted enones as single geometrical isomers. This transformation represents a completely atom economical alternative to the use of stabilized Wittig reagents in carbonyl olefination and may be viewed as a formal alkyne-carbonyl metathesis.

  DOI：

  10.1021/ol050838x
• 作为产物：
  描述：

  烯丙基-(3-苯基-2-丙炔)基丙二酸二乙酯 在 臭氧 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 以68%的产率得到2-(2-oxoethyl)-2-(3-phenylprop-2-ynyl)malonic acid diethyl ester
  参考文献：
  名称：

  Alkynes as Synthetic Equivalents to Stabilized Wittig Reagents:  Intra- and Intermolecular Carbonyl Olefinations Catalyzed by Ag(I), BF₃, and HBF₄

  摘要：

  The first use of cationic silver (AgSbF4) as a catalyst for intra- and intermolecular alkyne-carbonyl coupling to form conjugated enones is described, and a comparison to corresponding Bronsted acid (HBF4) and Lewis acid (BF3) catalyst systems is made. Notably, intermolecular coupling proceeds stereoselectively to afford the corresponding trisubstituted enones as single geometrical isomers. This transformation represents a completely atom economical alternative to the use of stabilized Wittig reagents in carbonyl olefination and may be viewed as a formal alkyne-carbonyl metathesis.

  DOI：

  10.1021/ol050838x

文献信息

• Dual Photoredox/Cobalt-Catalyzed Reductive Cyclization of Alkynals
  作者：Kento Nakamura、Hina Nishigaki、Yoshihiro Sato

  DOI：10.1021/acscatal.3c06206

  日期：2024.3.1

  alkynals using H2O for the catalyst turnover. This method was applied to aliphatic and aromatic aldehydes for five-, six-, and seven-membered (heterocyclic) ring formation with various substitutions on alkyne units. This H2O-added protocol was further developed into a one-pot transformation from acetals through in situ generated aldehydes, which shortened the synthetic path of the reaction.

  取代环醇是药学上必需的支架之一。在这里，我们报道了使用 H 2 O进行催化剂周转的光氧化还原/钴催化的炔醛还原环化。该方法适用于脂肪族和芳香族醛，形成五元、六元和七元（杂环）环，并在炔单元上进行各种取代。这种添加H 2 O的方案进一步发展为从缩醛到原位生成醛的一锅转化，从而缩短了反应的合成路径。
• Butenolide Synthesis by Molybdenum-Mediated Hetero-Pauson−Khand Reaction of Alkynyl Aldehydes
  作者：Javier Adrio、Juan C. Carretero

  DOI：10.1021/ja0684186

  日期：2007.1.1

  The highly reactive complex Mo(CO)(3)(DMF)(3) promotes the CO gas-free cyclocarbonylation of 1,5- and 1,6-alkynyl aldehydes under very mild reaction conditions to provide fused butenolides in good yields. This novel Mo-mediated hetero-Pauson-Khand reaction is very general with regard to the substitution at the alkyne terminus and tether (18 tested cases). Using readily available chiral alkynyl aldehydes, this procedure has been applied to the enantio- and stereoselective synthesis of highly substituted bicyclic butenolides, including an intermediate in natural product synthesis.
• Ru₃(CO)₁₂-Catalyzed Cyclocarbonylation of Yne-Aldehydes to Bicyclic α,β-Unsaturated γ-Butyrolactones
  作者：Naoto Chatani、Tsumoru Morimoto、Yoshiya Fukumoto、Shinji Murai

  DOI：10.1021/ja9802697

  日期：1998.6.1
• Alkynes as Synthetic Equivalents to Stabilized Wittig Reagents:  Intra- and Intermolecular Carbonyl Olefinations Catalyzed by Ag(I), BF₃, and HBF₄
  作者：Jong Uk Rhee、Michael J. Krische

  DOI：10.1021/ol050838x

  日期：2005.6.1

  The first use of cationic silver (AgSbF4) as a catalyst for intra- and intermolecular alkyne-carbonyl coupling to form conjugated enones is described, and a comparison to corresponding Bronsted acid (HBF4) and Lewis acid (BF3) catalyst systems is made. Notably, intermolecular coupling proceeds stereoselectively to afford the corresponding trisubstituted enones as single geometrical isomers. This transformation represents a completely atom economical alternative to the use of stabilized Wittig reagents in carbonyl olefination and may be viewed as a formal alkyne-carbonyl metathesis.