4-(tert-butyl)phenyl 3-phenylpropiolate | 267901-39-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: 4-(tert-butyl)phenyl 3-phenylpropiolate
• 英文别名: 4'-tert-butylphenyl phenylpropiolate；(4'-t-Butylphenyl)phenylpropiolate；(4-tert-butylphenyl) 3-phenylprop-2-ynoate
• CAS: 267901-39-3
• 化学式: C₁₉H₁₈O₂
• 分子量: 278.351
• InChiKey: WFAJZJWMAYCSKD-UHFFFAOYSA-N

物化性质

• 熔点：
  91-93 °C
• 沸点：
  391.0±25.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(tert-butyl)phenyl 3-phenylpropiolate 在 palladium diacetate 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以70%的产率得到4-phenyl-6-tert-butylcoumarin
  参考文献：
  名称：

  New Method for Preparation of Coumarins and Quinolinones via Pd-Catalyzed Intramolecular Hydroarylation of C−C Triple Bonds

  摘要：

  A new and general method has been developed for preparation of coumarins and quinolinones by intramolecular hydroarylation of alkynes. Various aryl alkynoates and alkynanilides undergo fast intramolecular reaction at room temperature in the presence of a catalytic amount of Pd(OAc)(2) in a mixed solvent containing trifluoroacetic acid (TFA), affording coumarins and quinolinones in moderate to excellent yields with more than 1000 turnover numbers (TON) to Pd. The methodology proved to tolerate a number of functional groups such as Br and CHO. On the basis of isotope experiments, a possible mechanism involving ethynyl chelation-assisted electrophilic metalation of aromatic C-H bonds by in-situ generated cationic Pd(II) species has been discussed. Also the involvement of vinylcationic species has been suggested.

  DOI：

  10.1021/jo000861q
• 作为产物：
  描述：

  碘苯 在 4-二甲氨基吡啶 、 四(三苯基膦)钯 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 24.0h， 生成 4-(tert-butyl)phenyl 3-phenylpropiolate
  参考文献：
  名称：

  可见光诱导硒自由基介导的 1,4-芳基迁移过程中产物选择性的变化

  摘要：

  在此，我们展示了可见光诱导的硒自由基介导的芳基炔酸酯的多米诺骨牌反应，用于合成 1,1-二硒化物烯烃衍生物和含硒 α,β-不饱和羧酸。该工艺温和、不含金属、易于处理且可扩展。脱羧步骤可以通过应用催化量的曙红 Y 染料和碳酸铯作为碱来控制。该方法显示出良好的官能团耐受性，并提供了不错的产品产量。此外，通过制备烯丙醇、α、β-不饱和酯和乙烯基卤化物，进一步扩展了该协议的合成效用。

  DOI：

  10.1021/acs.orglett.2c03260
• 作为试剂：
  描述：

  2,2,6,6-四甲基哌啶氧化物 、 二氟溴乙酸乙酯 在 fac-Ir(ppy)₃ 、 potassium carbonate 、 4-(tert-butyl)phenyl 3-phenylpropiolate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 生成 ethyl 2,2-difluoro-2-((2,2,6,6-tetramethylpiperidin-1-yl)oxy)acetate
  参考文献：
  名称：

  Visible-Light-Mediated Radical Aryldifluoroacetylation of Alkynes with Ethyl Bromodifluoroacetate for the Synthesis of 3-Difluoroacetylated Coumarins

  摘要：

  A mild and efficient method for the synthesis of 3-difluoroacetylated coumarins through visible-light-promoted aryldifluoroacetylation of alkynes with ethyl bromodifluoroacetate has been developed. The reaction allows the direct formation of C-sp(2)-CF2COOEt and C-C bonds via a proposed tandem radical cyclization process.

  DOI：

  10.1021/acs.joc.5b00305

文献信息

• Visible Light-Induced Decarboxylative Acylarylation of Phenyl Propiolates with α-Oxocarboxylic Acids to Coumarins Catalyzed by Hypervalent Iodine Reagents under Transition Metal-Free Conditions
  作者：Shuai Yang、Hui Tan、Wangqin Ji、Xiangbiao Zhang、Pinhua Li、Lei Wang

  DOI：10.1002/adsc.201600721

  日期：2017.2.2

  No Abstract

  没有摘要
• Visible-Light-Promoted Dual C–C Bond Formations of Alkynoates via a Domino Radical Addition/Cyclization Reaction: A Synthesis of Coumarins
  作者：Shangbiao Feng、Xingang Xie、Weiwei Zhang、Lin Liu、Zhuliang Zhong、Dengyu Xu、Xuegong She

  DOI：10.1021/acs.orglett.6b01857

  日期：2016.8.5

  difunctionalization of alkynoates has been accomplished. This procedure provides a new strategy toward synthesis of the coumarin core structure by photoredox-mediated oxidation to generate the α-oxo radical, which supervenes a domino radical addition/cyclization reaction in moderate to good yields with high regioselectivity at ambient temperature.

  已经实现了可见光促进的炔属酸酯的温和直接双官能化。该方法为通过光氧化还原介导的氧化合成香豆素核心结构以产生α-氧代自由基提供了新的策略，该α-氧代自由基在环境温度下以中等至良好的产率，高产率地取代了多米诺骨牌自由基加成/环化反应。
• An efficient light on–off one-pot method for the synthesis of 3-styryl coumarins from aryl alkynoates
  作者：Hongjun Kong、Qingrui Li、Yunnian Yin、Mengmeng Huang、Jung Keun Kim、Yu Zhu、Yabo Li、Yangjie Wu

  DOI：10.1039/c9ob00421a

  日期：——

  An efficient one-pot stepwise method to synthesize 3-styryl-4-arylcoumarins from simple alkynoates is demonstrated. On the basis of the control experiments, a possible mechanism involving light-driven radical cyclization and Pd-catalysed cross-coupling processes for this synthesis method is proposed. The results of X-ray analysis and spectroscopy experiments prove that the substituent effect has a

  演示了一种有效的一锅式逐步方法，可从简单的炔烃中合成3-苯乙烯基-4-芳基香豆素。在控制实验的基础上，提出了一种可能的机理，涉及该合成方法的光驱动自由基环化和Pd催化的交叉偶联过程。X射线分析和光谱实验的结果证明，取代基效应对合成的3-苯乙烯基香豆素的吸收和发射性能有显着影响。
• Visible-light initiated oxidative cyclization of phenyl propiolates with sulfinic acids to coumarin derivatives under metal-free conditions
  作者：Wenchao Yang、Shuai Yang、Pinhua Li、Lei Wang

  DOI：10.1039/c5cc00878f

  日期：——

  A visible-light initiated oxidative cyclization of phenyl propiolates with sulfinic acids has been developed at room temperature under metal-free conditions.

  已在室温下无金属条件下开发了苯基丙炔酸酯与亚砜酸的可见光引发氧化环化反应。
• The visible-light-induced acylation/cyclization of alkynoates with acyl oximes for the construction of 3-acylcoumarins
  作者：Quan Zhou、Fang-Ting Xiong、Pu Chen、Bi-Quan Xiong、Ke-Wen Tang、Yu Liu

  DOI：10.1039/d1ob01568k

  日期：——

  by the visible-light-induced acylation/cyclization of alkynoates with various acyl oxime compounds in acetonitrile. The difunctionalization of carbon–carbon triple bonds precedes the generation of iminyl radicals, which is followed by the formation of acyl radicals. The acyl radicals then attack the carbon–carbon triple bonds, followed by 5-exo-trig cyclization and 1,2-ester migration. This strategy

  描述了一种以氮为中心的自由基介导的碳-碳键断裂策略来合成功能化的 3-酰基香豆素。该策略是通过可见光诱导的炔酸酯与乙腈中的各种酰基肟化合物的酰化/环化来实现的。碳-碳三键的双官能化先于亚氨基自由基的产生，然后是酰基自由基的形成。然后酰基自由基攻击碳-碳三键，然后进行 5 -exo-trig环化和 1,2-酯迁移。该策略具有广泛的底物适应性和良好的取代基耐受性。