ethyl 3-(3-ethoxy-3-oxoprop-1-yn-1-yl)benzoate

• 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: ethyl 3-(3-ethoxy-3-oxoprop-1-yn-1-yl)benzoate
• 英文别名: Ethyl 3-(3-ethoxy-3-oxoprop-1-ynyl)benzoate；ethyl 3-(3-ethoxy-3-oxoprop-1-ynyl)benzoate
• 化学式: C₁₄H₁₄O₄
• 分子量: 246.263
• InChiKey: ZFKZYPVBZIASLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 3-(3-ethoxy-3-oxoprop-1-yn-1-yl)benzoate 、 联硼酸频那醇酯 在 三丁基膦 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以83%的产率得到(E)-ethyl 3-(3-ethoxy-3-oxo-1,2-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-propen-1-yl)benzoate
  参考文献：
  名称：

  Anti-Selective Vicinal Silaboration and Diboration of Alkynoates through Phosphine Organocatalysis

  摘要：

  Trialkylphosphine organocatalysts have enabled anti-selective vicinal silaboration and diboration of the C-C triple bond in alkynoates to produce beta-boryl-alpha-silyl acrylates and alpha,beta-diboryl acrylates, respectively. The anti stereoselectivity was complete and robust. A variety of functional groups were tolerated in the alkynoates. The two vicinally installed heteroatom substituents of the beta-boryl-alpha-silyl acrylates and alpha,beta-diboryl acrylates could be differentiated and transformed in a stepwise manner, allowing the synthesis of a diverse array of unsymmetrical tetrasubstituted alkenes.

  DOI：

  10.1021/acs.orglett.5b00305
• 作为产物：
  描述：

  3-碘苯甲酸甲酯 、 丙炔酸乙酯 在 bis-triphenylphosphine-palladium(II) chloride 、 potassium carbonate 、 copper(l) iodide 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以61%的产率得到ethyl 3-(3-ethoxy-3-oxoprop-1-yn-1-yl)benzoate
  参考文献：
  名称：

  的内部炔烃的抗氢芳基化：钯和能量转移催化的合并。

  摘要：

  据报道，与贫电子和富电子芳基试剂均兼容的缺电子内部炔烃的一般催化抗氢芳基化反应。这种选择性是通过Ar-Pd分子对炔烃进行顺式羰基缩合，然后进行Ir串联的Ir光催化逆热力学E → Z异构化来实现的。邻取代的硼酸的使用使得能够经由级联过程直接进入药学上相关的杂环核。提供了有关Ar–Pd与Pd–H作为活性物种参与的机理的见解。

  DOI：

  10.1021/acs.orglett.0c02281

文献信息

• Phosphine-Catalyzed Vicinal Acylcyanation of Alkynoates
  作者：Hiroaki Murayama、Kazunori Nagao、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/acs.orglett.6b00677

  日期：2016.4.1

  Phosphine organocatalysis enabled vicinal acylcyanation of alkynoates with acyl cyanides to form acrylonitrile derivatives with a tetrasubstituted alkene moiety. The acyl and cyano groups were introduced at the α and β carbon atoms, respectively, of the C–C triple bond in the alkynoates with complete regioselectivity and high anti stereoselectivity. A variety of functional groups in the acyl cyanides

  膦有机催化能够使炔酸酯与酰基氰化物一起进行邻位酰基氰化，以形成具有四取代烯烃部分的丙烯腈衍生物。酰基和氰基分别在炔烃的C–C三键的α和β碳原子处引入，具有完全的区域选择性和高的立体抗选择性。酰基氰化物和炔酸中的多种官能团是可以耐受的。
• Phosphine-Catalyzed <i>Anti</i>-Hydroboration of Internal Alkynes
  作者：Kazunori Nagao、Ayaka Yamazaki、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/acs.orglett.8b00390

  日期：2018.4.6

  Trialkylphosphine organocatalysts have enabled regioselective anti-hydroboration of internal, alkynes with pinacolborane reagents to provide (E)-disubstituted alkenylboronate compounds. The alkenyl-boronate can be used for derivatizations, such as protodeborylation, Suzuld-Miyaura coupling, conjugate reduction, and Diels-Alder reactions.
• Synthesis of Ethyl Arylpropiolates through Palladium-Catalyzed Cross-Coupling­ Reactions of Aryl Iodides with In Situ Generated Lithium Tetrakis(ethoxycarbonylethynyl)indates
  作者：Phil Lee、Youngchul Park、Dongjin Kang、Woo Jeon、Taekyu Ryu

  DOI：10.1055/s-0033-1339110

  日期：——
• <i>Anti</i>-Selective Vicinal Silaboration and Diboration of Alkynoates through Phosphine Organocatalysis
  作者：Kazunori Nagao、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/acs.orglett.5b00305

  日期：2015.3.6

  Trialkylphosphine organocatalysts have enabled anti-selective vicinal silaboration and diboration of the C-C triple bond in alkynoates to produce beta-boryl-alpha-silyl acrylates and alpha,beta-diboryl acrylates, respectively. The anti stereoselectivity was complete and robust. A variety of functional groups were tolerated in the alkynoates. The two vicinally installed heteroatom substituents of the beta-boryl-alpha-silyl acrylates and alpha,beta-diboryl acrylates could be differentiated and transformed in a stepwise manner, allowing the synthesis of a diverse array of unsymmetrical tetrasubstituted alkenes.
• <i>anti</i>-Hydroarylation of Activated Internal Alkynes: Merging Pd and Energy Transfer Catalysis
  作者：Javier Corpas、Pablo Mauleón、Ramón Gómez Arrayás、Juan C. Carretero

  DOI：10.1021/acs.orglett.0c02281

  日期：2020.8.21

  electron-poor and electron-rich aryl reagents is reported. This selectivity is achieved through a sequential syn-carbopalladation of the alkyne by an Ar–Pd species, followed by a tandem, Ir-photocatalyzed, counter-thermodynamic E → Z isomerization. The use of ortho-substituted boronic acids enables direct access to pharmaceutically relevant heterocyclic cores via a cascade process. Mechanistic insight

  据报道，与贫电子和富电子芳基试剂均兼容的缺电子内部炔烃的一般催化抗氢芳基化反应。这种选择性是通过Ar-Pd分子对炔烃进行顺式羰基缩合，然后进行Ir串联的Ir光催化逆热力学E → Z异构化来实现的。邻取代的硼酸的使用使得能够经由级联过程直接进入药学上相关的杂环核。提供了有关Ar–Pd与Pd–H作为活性物种参与的机理的见解。