tert-butyl 4-oxo-6-phenyl-3,4-dihydropyridine-1(2H)-carboxylate | 1284129-42-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: tert-butyl 4-oxo-6-phenyl-3,4-dihydropyridine-1(2H)-carboxylate
• 英文别名: t-butyl 4-oxo-6-phenyl-3,4-dihydropyridine-1(2H)-carboxylate；Tert-butyl 4-oxo-6-phenyl-2,3-dihydropyridine-1-carboxylate
• CAS: 1284129-42-5
• 化学式: C₁₆H₁₉NO₃
• 分子量: 273.332
• InChiKey: XWVCTSZRTRFYQZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl 4-oxo-6-phenyl-3,4-dihydropyridine-1(2H)-carboxylate 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 1.0h， 以78%的产率得到Tert-butyl 5-bromo-4-oxo-6-phenyl-2,3-dihydropyridine-1-carboxylate
  参考文献：
  名称：

  Gold-Mediated Synthesis and Functionalization of Chiral Halopyridones

  摘要：

  A rapid and efficient one-step halopyridone synthesis has been developed based on gold-catalyzed cyclization of beta-amino-ynone intermediates and halodeauration process.

  DOI：

  10.1021/jo400827b
• 作为产物：
  描述：

  Diazo-(N-tert-butoxycarbonylglycyl)methane 在 silver hexafluoroantimonate 、 正丁基锂 、 三苯基膦氯金 、 silver nitrate 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 1,2-二氯乙烷 为溶剂， 反应 4.5h， 生成 tert-butyl 4-oxo-6-phenyl-3,4-dihydropyridine-1(2H)-carboxylate
  参考文献：
  名称：

  Enantiospecific Synthesis of Pyridinones as Versatile Intermediates toward Asymmetric Piperidines

  摘要：

  The enantiospecific syntheses of pyridinones from amino acids via a gold-catalyzed strategy are reported. Excellent stereocontrol was observed during the cyclization. This approach provides a straightforward tool for further synthetic applications toward piperidines.

  DOI：

  10.1021/ol201698m

文献信息

• Catalytic Allylic Oxidation of Cyclic Enamides and 3,4-Dihydro-2<i>H</i>-Pyrans by TBHP
  作者：Yang Yu、Ranad Humeidi、James R. Alleyn、Michael P. Doyle

  DOI：10.1021/acs.joc.7b01163

  日期：2017.8.18

  intermediate allylic free radical two sites for oxidative product formation are possible, and the selectivity of the oxidative process varies with the heteroatom when R = H. Cyclic enamides produce 4-piperidones in good yields when R = alkyl or aryl, but oxidation of 2H-pyrans also gives alkyl cleavage products. Alternative catalysts for TBHP oxidations show comparable selectivities but give lower product

  叔丁基过氧化氢（水中70％TBHP）使用己内酰胺基己二酸酯催化的[Rh 2（cap）4 ]烯丙基氧化杂烯取代的环状烯烃，形成烯酮产物，该产物具有各种2-取代的环状酰胺和3,4-二氢- 2 H-吡喃。这些反应在温和的反应条件下发生，操作上易于实施，并且对于低至0.25mol％的催化剂负载量的产物形成有效。通过中间烯丙基自由基的杂原子稳定化，可以形成两个氧化产物位点，并且当R = H时，氧化过程的选择性随杂原子而变化。当R =烷基或芳基时，环酰胺会以高收率生成4-哌啶酮，但是2的氧化H-吡喃还产生烷基裂解产物。TBHP氧化的替代催化剂显示出可比的选择性，但产物收率较低。
• Accessing spiropiperidines from dihydropyridones through tandem triflation–allylation and ring-closing metathesis (RCM)
  作者：Naresh Gantasala、Corentin Fournet、Myriam Le Roch、Claudia Lalli、Srihari Pabbaraja、Nicolas Gouault

  DOI：10.1039/d3ob00545c

  日期：——

  allyltributylstannane onto dihydropyridones allowed for the formation of gem bis-alkenyl intermediates that were converted to the corresponding spirocarbocycles with excellent yields via ring closing metathesis. The vinyl triflate group generated on these 2-spiro-dihydropyridine intermediates could be successfully used as a chemical expansion vector for further transformations namely Pd-catalyzed cross-coupling

  开发了一种从二氢吡啶酮开始构建 2-螺哌啶部分的新方法。三氟甲磺酸酐促进烯丙基三丁基锡烷在二氢吡啶酮上的共轭加成允许形成偕双烯基中间体，该中间体通过闭环复分解以优异的产率转化为相应的螺碳环。这些 2-螺二氢吡啶中间体上生成的三氟甲磺酸乙烯酯基团可以成功地用作进一步转化（即 Pd 催化的交叉偶联反应）的化学膨胀载体。
• Examining the Scope of Deriving β-Aryl Enones from Enol Silanes as Ketone Equivalents <i>via</i> Pd(II)-Mediated Sequential Dehydrosilylation and Arylation
  作者：Subba Rao Polimera、Andivelu Ilangovan、Murugaiah A. M. Subbaiah

  DOI：10.1021/acs.joc.3c00502

  日期：2023.6.2

  Silyl enol ethers were examined as a masked source of saturated ketones to derive β-aryl enones and their derivatives by dehydrosilylation to generate enones in situ and subsequent oxidative arylation with arylboronic acids as transmetallation coupling partners using relayed Pd(II) catalysis in one pot under base-free conditions. Oxygen was found to be an efficient and green oxidant to enable both

  将甲硅烷基烯醇醚作为饱和酮的掩蔽源进行检测，通过脱氢硅烷化原位生成烯酮，然后使用中继 Pd(II) 催化在一锅中进行原位氧化芳基化和芳基硼酸作为金属转移偶联伙伴，从而衍生出 β-芳基烯酮及其衍生物。无碱基条件。氧气被发现是一种有效的绿色氧化剂，可以实现烯醇硅烷的脱氢硅烷化和芳基化。此外，芳基化条件可以定制设计，以利用芳基卤化物作为芳基化剂的替代来源。通过 35 个实例（收率高达 95%）研究了制备范围，并且机理研究暗示了基于阳离子 Pd(II) 的催化体系。
• Synthesis and Chemoinformatic Analysis of Fluorinated Piperidines as 3D Fragments for Fragment-Based Drug Discovery
  作者：Myriam Le Roch、Jacques Renault、Gilles Argouarch、Elena Lenci、Andrea Trabocchi、Thierry Roisnel、Nicolas Gouault、Claudia Lalli

  DOI：10.1021/acs.joc.4c00143

  日期：2024.4.5

  then been evaluated by chemoinformatic tools. In particular, the compounds' pKa's have been calculated, revealing that the fluorine atoms notably lowered their basicity, which is correlated to the affinity for hERG channels resulting in cardiac toxicity. The “lead-likeness” and three-dimensionality have also been evaluated to assess their ability as useful fragments for drug design. A random screening

  已经描述了从容易获得的二氢吡啶酮衍生物中简明合成小型氟化哌啶库。然后通过化学信息学工具评估氟化对不同位置的影响。特别是，计算了化合物的pKa值，表明氟原子显着降低了它们的碱性，这与导致心脏毒性的 hERG 通道的亲和力相关。还对“先导相似性”和三维度进行了评估，以评估它们作为药物设计有用片段的能力。然后对一组代表性蛋白水解酶进行随机筛选，结果发现一个支架被 3CL Pro （SARS-CoV-2 冠状病毒的主要蛋白酶）的催化口袋识别。
• Pd-Diimine: A Highly Selective Catalyst System for the Base-Free Oxidative Heck Reaction
  作者：Aditya L. Gottumukkala、Johannes F. Teichert、Dorus Heijnen、Niek Eisink、Simon van Dijk、Catalina Ferrer、Adri van den Hoogenband、Adriaan J. Minnaard

  DOI：10.1021/jo101942f

  日期：2011.5.6

  Pd(OAc)(2)/3 is an efficient catalyst system for the base-free oxidative Heck reaction that outperforms the currently available catalysts for the more challenging substrates studied. The catalyst system is highly selective, and works at room temperature with dioxygen as the oxidant.