4-phenyl-6-tert-butylcoumarin

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 新黄酮类化合物
• 英文名称: 4-phenyl-6-tert-butylcoumarin
• 英文别名: 6-(tert-butyl)-4-phenyl-2H-chromen-2-one；6-t-Butyl-4-phenylcoumarin；6-tert-butyl-4-phenylchromen-2-one
• 化学式: C₁₉H₁₈O₂
• 分子量: 278.351
• InChiKey: SSKQNLVCWFVYMD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• 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：

  Langlois reagent 、 4-phenyl-6-tert-butylcoumarin 在 dipotassium hydrogenphosphate 作用下， 以 丙酮 为溶剂， 反应 12.0h， 以67%的产率得到6-t-butyl-4-phenyl-3-(trifluoromethyl)-2H-1-benzopyran-2-one
  参考文献：
  名称：

  香豆素的绿色和无过渡金属的光介导的三氟甲基化反应

  摘要：

  描述了一种简单，无金属和氧化剂的光催化策略，用于在氙气灯照射下，使用廉价的三氟甲酸钠（Langlois试剂，CF 3 SO 2 Na）作为CF 3源直接对香豆素进行三氟甲基化。反应在环境条件下进行，并以中等收率得到相应的产物。丙酮可用作低成本的自由基引发剂，可从三氟甲磺酸钠高效生成CF 3自由基。

  DOI：

  10.1016/j.jfluchem.2018.08.003
• 作为产物：
  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

文献信息

• Copper/Selectfluor-System-Catalyzed Dehydration-Oxidation of Tertiary Cyclo­alcohols: Access to β-Substituted Cyclohex-2-enones, 4-Arylcoumarins, and Bi­aryls
  作者：Shaobo Ren、Jian Zhang、Jiahui Zhang、Heng Wang、Wei Zhang、Yunkui Liu、Miaochang Liu

  DOI：10.1002/ejoc.201500610

  日期：2015.8

  A route to β-substituted cyclohex-2-enones, 4-arylcoumarins, and biaryls has been developed. This approach involves a one-pot Cu0/Selectfluor-catalyzed dehydration–oxidation of tertiary cycloalcohols. Thus, by using 2 equiv. of Selectfluor at 25 °C, the dehydration–oxidation of tertiary cyclohexanols and oxabenzocyclohexanols gave β-substituted cyclohex-2-enones and 4-arylcoumarins, respectively; whereas

  β-取代的环己-2-烯酮、4-芳基香豆素和联芳基的路线已经开发出来。这种方法涉及一锅 CuO/Selectfluor 催化的叔环醇脱水氧化。因此，通过使用 2 equiv。Selectfluor 在 25 °C 下，叔环己醇和氧杂苯并环己醇的脱水-氧化分别得到 β-取代的环己-2-烯酮和 4-芳基香豆素；而叔环己醇的脱水-氧化使用 2.5 当量得到联芳基化合物作为最终产物。Selectfluor 在 80 °C。
• Metal-free annulative hydrosulfonation of propiolate esters: synthesis of 4-sulfonates of coumarins and butenolides
  作者：Rodney A. Fernandes、Ashvin J. Gangani、Rupesh A. Kunkalkar

  DOI：10.1039/c9nj06438a

  日期：——

  An efficient metal-free and cost-effective method for the synthesis of coumarin and butenolide 4-sulfonates has been developed involving addition of sulfonic acids to ethyl propiolates followed by lactonization.

  已开发出一种高效的无金属、成本效益的方法，用于合成香豆素和丁烯内酯4-磺酸酯，涉及将磺酸加入乙基丙炔酸酯，然后进行内酯化。
• Straightforward Entry toward Highly Substituted 2,3-Dihydrobenz[<i>b</i>]oxepines by Ring Expansion of Benzopyryliums with Donor–Acceptor Diazo Compounds
  作者：Thibaut Courant、Morgane Pasco、Thomas Lecourt

  DOI：10.1021/acs.orglett.8b00984

  日期：2018.5.4

  Ylide-type reactivity of diazo compounds is exploited in a new way to prepare benzo[b]oxepines thanks to the formation of three chemical bonds and two contiguous and highly substituted stereocenters in a single pot. This cationic reaction cascade first involves addition of a donor–acceptor-substituted diazo compound to a benzopyrylium. Selective 1,2 migration of the endocyclic C–C bond then results

  由于在单个罐中形成了三个化学键和两个连续且高度取代的立体中心，重氮化合物的Ylide型反应性被以一种新的方式用于制备苯并[ b ]氧杂环丁烷。这种阳离子反应级联首先涉及将供体-受体取代的重氮化合物添加到苯并吡啶中。内环C–C键的选择性1,2迁移随后导致环扩展并生成第二个氧碳鎓，该碳鎓被依次添加的亲核试剂捕获。
• Efficient Functionalization of Aromatic C−H Bonds Catalyzed by Gold(III) under Mild and Solvent-Free Conditions
  作者：Zhangjie Shi、Chuan He

  DOI：10.1021/jo0497353

  日期：2004.5.1

  A gold(III)-catalyzed carbon-carbon bond formation reaction between arenes and electron-deficient alkynes or alkenes is described. Electron-rich arenes can be efficiently functionalized with the alkyne or alkene substrates. This reaction can be run with neat reactants at ambient temperature. Under the "solventless" conditions, clean product was obtained from a reaction of equal molar amounts of arene and alkyne substrates. The mild conditions and potential tolerance to different functional groups make this method practical for arene functionalization and for constructing complicated molecules. Efficient preparation of various coumarins from aryl alkynoates was demonstrated. Preliminary mechanistic studies were performed to probe the pathway of this reaction.
• Novel Pd(II)- and Pt(II)-Catalyzed Regio- and Stereoselective <i>trans</i>-Hydroarylation of Alkynes by Simple Arenes
  作者：Chengguo Jia、Wenjun Lu、Juzo Oyamada、Tsugio Kitamura、Kenji Matsuda、Masahiro Irie、Yuzo Fujiwara

  DOI：10.1021/ja0005845

  日期：2000.8.1

  Efficient trans-hydroarylation of alkynes by simple arenes has been realized regio- and stereoselectively at room temperature in the presence of Pd(II) or Pt(II) catalysts and a mixed solvent containing trifluoroacetic acid (TFA). Various arenes undergo trans-hydroarylation selectively across terminal and internal C-C triple bonds-including those conjugated to CHO, COMe, CO2H, and CO2Et groups, affording kinetically controlled cis-arylalkenes predominantly in most cases, especially, in good yields for electron-rich arenes and activated alkynes. The formation of arene/alkyne 1/2 or 2/1 adducts as side products is dependent on the arenes' and alkynes' substituents, which can be suppressed in some cases by changing the catalyst, catalyst concentration, and reaction time. The Pt(II) system, PtCl2/2AgOAc/TFA, shows lower catalytic activity than Pd(OAc)(2)/TFA, but higher selectivity, giving higher yields of adducts at the same conversion. On the basis of several isotope experiments and control reactions, a possible mechanism involving electrophilic metalation of aromatic C-H bonds by in-situ-generated cationic Pd(II) and Pt(II) species leading to intermolecular trans-arylpalladation to alkynes has been discussed.