2-(4-phenyl-3-hexynyl)malonic acid diethyl ester | 440095-53-4

• 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-(4-phenyl-3-hexynyl)malonic acid diethyl ester
• 英文别名: diethyl 2-(4-phenylbut-3-yn-1-yl)malonate
• CAS: 440095-53-4
• 化学式: C₁₇H₂₀O₄
• 分子量: 288.343
• InChiKey: TYYRZROLBJFCCY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.56
• 重原子数：
  21.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-(4-phenyl-3-hexynyl)malonic acid diethyl ester 在 硫酸 、 水 、 sodium hydroxide 作用下， 以 甲醇 为溶剂， 生成 2,2-dimethyl-5-(4-phenylbut-3-yn-1-yl)-1,3-dioxane-4,6-dione
  参考文献：
  名称：

  Radical Cyclization Cascades of Unsaturated Meldrum’s Acid Derivatives

  摘要：

  Unsaturated, differentially substituted Meldrum's acid derivatives undergo cascade cyclizations upon ester reduction with Sml(2)-H2O. The cascade cyclizations proceed in good yield and with high diastereocontrol and convert simple, achiral starting materials to complex molecular architectures, bearing up to four stereocenters, In a single operation. The cascades are triggered by the generation and trapping of unusual radical-anions formed by electron transfer to the ester carbonyl.

  DOI：

  10.1021/ol2029367
• 作为产物：
  描述：

  sodium methanetricarboxylic acid triethyl ester 在 sodium ethanolate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 生成 2-(4-phenyl-3-hexynyl)malonic acid diethyl ester
  参考文献：
  名称：

  An Allenic Pauson−Khand-Type Reaction:  A Reversal in π-Bond Selectivity and the Formation of Seven-Membered Rings

  摘要：

  [GRAPHICS]Treatment of alkynyl allenes with [Rh(CO)(2)Cl](2) results in a formal [2 + 2 + 1] cycloaddition reaction. This reaction occurs with complete regioselectivity for a variety of substrates affording only 4-alkylidene cyclopentenones in good yields. Moreover, seven-membered rings have been prepared in high yields.

  DOI：

  10.1021/ol025955w

文献信息

• Palladium‐Catalyzed [2+2+1] Spiroannulation via Alkyne‐Directed Remote C−H Arylation and Subsequent Arene Dearomatization
  作者：Zhijun Zuo、Jing Wang、Jingjing Liu、Yaoyu Wang、Xinjun Luan

  DOI：10.1002/anie.201909557

  日期：2020.1.7

  Palladium-catalyzed alkene-directed cross-coupling of aryl iodide with another aryl halide through C-H arylation opens a unique avenue for unsymmetrical biaryl-derived molecules. However, homo-coupling of aryl iodides often erodes the overall synthetic efficiency. Reported herein is a highly chemoselective Pd0 -catalyzed alkyne-directed cross-coupling of aryl iodides with bromophenols, which was subsequently

  通过CH芳基化反应，钯催化的芳基碘化物与另一种芳基卤化物的烯烃定向交叉偶联为不对称联芳基衍生的分子开辟了一条独特的途径。但是，芳基碘化物的均偶联通常会损害整体合成效率。本文报道的是芳基碘化物与溴酚的高度化学选择性的Pd0催化的炔烃定向的交叉偶联，其后随后进行苯酚脱芳香化以提供非常有吸引力的[2 + 2 + 1]螺环化。值得注意的是，根本没有观察到芳基碘的可能的均偶联。机理研究表明，五元芳基/乙烯基palladacycle最有可能促进了联芳基交叉偶联的关键步骤。
• Gold‐Catalyzed Desymmetric Lactonization of Alkynylmalonic Acids Enabled by Chiral Bifunctional P,N ligands
  作者：Bijin Lin、Tilong Yang、Dequan Zhang、Yang Zhou、Liangliang Wu、Jingfei Qiu、Gen‐Qiang Chen、Chi‐Ming Che、Xumu Zhang

  DOI：10.1002/anie.202201739

  日期：2022.6.7

  The gold-catalyzed desymmetrization of alkynylmalonic acids proceed smoothly to give chiral lactones with high yield and ee. Control experiments and DFT calculations indicate that the amino group of the ligands and the alcohol additives play key roles in the control of enantioselectivity.

  金催化的炔基丙二酸去对称化反应顺利进行，得到高收率和ee的手性内酯。对照实验和 DFT 计算表明，配体的氨基和醇添加剂在对映选择性的控制中起关键作用。
• Accessing Benzoazepine Derivatives via Photoinduced Radical Relay Formal [5 + 2] Reaction of Amide/Alkyne Enabled by Palladium Catalysis
  作者：Yu-jia Du、Xia-xin Sheng、Lu-ning Tang、Jia-ming Chen、Guo-ying Liu、Hao Hu、Sen Yang、Lei Zhu、Ming Chen

  DOI：10.1021/acs.orglett.4c00979

  日期：2024.4.5

  synthesizes biologically active compounds. Notably, the resulting tricyclic benzo[b]azepines offer diversification opportunities through simple transformations. DFT calculations elucidate a seven-membered ring closure mechanism involving the alkenyl radical and Pd(I) rebound alongside a concerted metalation–deprotonation (CMD) process.

  一类新型炔烃酰胺促进了前所未有的光诱导钯催化自由基中继形式 [5 + 2] 反应。这种创新策略可以快速构建多种稠合苯并氮杂卓结构，产生结构新颖且引人注目的化合物。该方法具有广泛的底物范围和出色的官能团耐受性，可合成生物活性化合物。值得注意的是，所得的三环苯并[ b ]氮杂卓通过简单的转化提供了多样化的机会。 DFT 计算阐明了涉及烯基自由基和 Pd(I) 反弹以及协同金属化-去质子化 (CMD) 过程的七元闭环机制。