3,5-dimethyl-2,4-diphenylpyridine

• 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: 3,5-dimethyl-2,4-diphenylpyridine
• 化学式: C₁₉H₁₇N
• 分子量: 259.351
• InChiKey: VPUMIAYWHDKAKK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (Z)-3-iodo-2-methyl-3-phenyl-2-propenal 在 palladium diacetate 、 水 、 sodium carbonate 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 3,5-dimethyl-2,4-diphenylpyridine
  参考文献：
  名称：

  Synthesis of Isoquinolines and Pyridines by the Palladium-Catalyzed Iminoannulation of Internal Alkynes

  摘要：

  A wide variety of substituted isoquinoline, tetrahydroisoquinoline, 5,6-dihydrobenz[f]isoquinoline, pyrindine, and pyridine heterocycles have been prepared in good to excellent yields via annulation of internal acetylenes with the tert-butylimines of o-iodobenzaldehydes and 3-halo-2-alkenals in the presence of a palladium catalyst. The best results are obtained by employing 5 mol % of Pd(OAc)(2), an excess of the alkyne, 1 equiv of Na2CO3 as a base, and 10 mol % of PPh3 in DMF as the solvent. This annulation methodology is particularly effective for aryl- or alkenyl-substituted alkynes. When electron-rich imines are employed, this chemistry can be extended to alkyl-substituted alkynes. Trimethylsilyl-substituted alkynes also undergo this annulation process to afford monosubstituted heterocyclic products absent the silyl group.

  DOI：

  10.1021/jo0105540

文献信息

• Ammonium iodide-promoted cyclization of ketones with DMSO and ammonium acetate for synthesis of substituted pyridines
  作者：Xiaojun Pan、Qiao Liu、Liming Chang、Gaoqing Yuan

  DOI：10.1039/c5ra07584j

  日期：——

  A simple and efficient method has been developed for the synthesis of symmetrical and unsymmetrical pyridines via NH4I-promoted cyclization of ketones with DMSO and NH4OAc. It was found that methyl ketones always gave selective formation of the unsymmetrical pyridine, while non-methyl ketones gave unpredictable results (symmetrical or non-symmetrical product only, or a mixture of the two). In addition

  已经开发了一种简单有效的方法，用于通过DMSO和NH 4 OAc通过NH 4 I促进的酮的环化反应来合成对称和不对称吡啶。发现甲基酮总是选择性地形成不对称吡啶，而非甲基酮则产生不可预测的结果（仅对称或不对称产物，或两者的混合物）。另外，氘标记实验表明目标产物吡啶环的C4或C6是由DMSO产生的。
• Ruthenium Complexes Immobilized on Functionalized Knitted Hypercrosslinked Polymers as Efficient and Recyclable Catalysts for Organic Transformations
  作者：Zhifang Jia、Kewei Wang、Bien Tan、Yanlong Gu

  DOI：10.1002/adsc.201600816

  日期：2017.1.4

  and effective catalyst for the synthesis of 2,4‐diaryl‐substituted pyridines from acetophenones, ammonium acetate (NH4OAc) and dimethylformamide (DMF), and the cycloaddition reaction of diazodicarbonyl compounds with olefins to afford dihydrofurans. In addition, a combination of HCP–PPh3–Ru and Amberlyst‐15 enabled us to establish a simple protocol for the direct synthesis of carbazole derivatives from

  通过一步外部交联反应，由苯和三苯膦（PPh 3）制备了高交联聚合物（HCP）固定化钌催化剂（HCP-PPh 3 -Ru）。催化剂的结构和组成已通过许多物理化学方法得到了充分表征。发现HCP–PPh 3 –Ru具有较高的Brunauer–Emmett–Teller（BET）表面积，大孔体积和低骨骼密度。此外，Ru催化剂还具有一些优点，例如合成成本低以及良好的化学和热稳定性。然后，将HCP–PPh 3 –Ru用作可回收和有效的催化剂，用于从苯乙酮，乙酸铵（NH 4OAc）和二甲基甲酰胺（DMF），以及重氮二羰基化合物与烯烃的环加成反应，生成二氢呋喃。此外，HCP–PPh 3 –Ru和Amberlyst-15的组合使我们能够建立一个简单的协议，用于由重氮二羰基化合物，烷基乙烯基醚和吲哚直接合成咔唑衍生物。在这些选择的反应中，催化剂容易回收并重复使用数次而没有明显的活性损失。
• Modular Synthesis of Highly Substituted Pyridines via Enolate α-Alkenylation
  作者：Leo A. Hardegger、Jacqueline Habegger、Timothy J. Donohoe

  DOI：10.1021/acs.orglett.5b01312

  日期：2015.7.2

  enolate α-alkenylation of ketones is presented; the formation of aromatic compounds is a new direction for this catalytic C–C bond forming reaction. In the key step, a protected β-haloalkenylaldehyde participates in α-alkenylation with a ketone to afford a 1,5-dicarbonyl surrogate, which then undergoes cyclization/double elimination to the corresponding pyridine product, all in one pot. The β-haloalkenylaldehyde

  提出了一种基于钯催化酮的​​烯醇化α-烯基化反应的高取代吡啶合成的新方法。芳族化合物的形成是该催化性CC键形成反应的新方向。在关键步骤中，受保护的β-卤代烯醛与酮一起参与α-烯基化反应，以提供1,5-二羰基替代物，然后对其进行环化/双消除反应，形成相应的吡啶产物，全部集中在一个罐中。β-卤代烯基醛原料可以通过Vilsmeier卤代甲酰基化从相应的亚甲基酮获得。使用这种简洁的方法，可以从市售化合物的三个步骤中合成出各种高度取代的吡啶。
• Pd-Catalyzed Decarboxylation and Dual C(sp³)–H Functionalization Protocols for the Synthesis of 2,4-Diarylpyridines
  作者：Raghuram Gujjarappa、Nagaraju Vodnala、Mohan Kumar、Chandi C. Malakar

  DOI：10.1021/acs.joc.8b02971

  日期：2019.5.3

  The Pd-catalyzed decarboxylation and dual C(sp3)–H bond functionalization approaches have been described for the preparation of symmetrical and unsymmetrical 2,4-diarylpyridines. The developed transformations were realized using nonactivated aromatic ketones and amino acids as C–N sources. The efficacy of the catalyst and reagent combination drives the transformation toward the formation of desired

  Pd催化的脱羧作用和双重C（sp 3）–H键官能化方法已被描述用于制备对称和不对称的2,4-二芳基吡啶。使用非活化的芳族酮和氨基酸作为C–N来源可以实现发达的转化。催化剂和试剂组合的功效推动了向高产率和高选择性的所需产物形成的转化。所描述的反应条件通过[2 + 2 + 2]环加成诱导了苯丙氨酸的自反应，并最小化了3,5-苯基吡啶作为副产物的形成，而使用甘氨酸作为C–N来源，相应的2， 6-二芳基吡啶是次要产物。
• Decarboxylative cyclization of amino acids towards the Regioselective synthesis of 2,4-diarylpyridines via relay Fe(III)/In(III)-catalysis
  作者：Raghuram Gujjarappa、Nagaraju Vodnala、Chandi C. Malakar

  DOI：10.1016/j.tetlet.2019.151495

  日期：2020.2

  A competent relay Fe(III)-/In(III)-catalyzed decarboxylative cyclization of amino acids has been devised towards the exclusive preparation of 2,4-diarylpyridines. The efficacy of the developed conditions drives the reaction towards selective formation of 2,4-diarylpyridines over other pyridine derivatives. The described protocol showed good functional group tolerance with moderate to good yields of

  已设计出一种能胜任的Fe（III）-/ In（III）催化的氨基酸脱羧环化反应，以专门制备2,4-二芳基吡啶。所开发条件的功效驱使反应朝着比其他吡啶衍生物选择性地形成2，4-二芳基吡啶的方向发展。所描述的方案显示出良好的官能团耐受性，产品的产率中等至良好。