4-methyl-5-(pyridin-3-yl)thiazole

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4-methyl-5-(pyridin-3-yl)thiazole
• 英文别名: 3-(4-Methylthiazol-5-yl)-pyridine；4-methyl-5-pyridin-3-yl-1,3-thiazole
• 化学式: C₉H₈N₂S
• 分子量: 176.242
• InChiKey: FRKSHFPYIOLJSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4-甲基噻唑 、 3-溴吡啶 在 {N,N-(1,2-diphenylethane-1,2-diylidene)bis(2-benzhydryl-4,6-dimthylaniline)}dichloropalladium 、 potassium carbonate 、 三甲基乙酸 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 12.0h， 以95%的产率得到4-methyl-5-(pyridin-3-yl)thiazole
  参考文献：
  名称：

  庞大的α-二亚胺钯配合物：在好氧条件下对杂芳烃直接进行C–H键芳基化反应非常有效†

  摘要：

  通过增强主链和N-芳基部分的体积的策略，我们设计并合成了一种体积较大的α-二亚胺钯配合物（即{[Ar–N C（R）–C（R）N– Ar] PdCl 2，（Ar ＝ 2-苯甲酰基-4，6-二甲基苯基）}，C1，R ＝ H；C2，R ＝ An；C3，R ＝ Ph）。这些钯配合物的结构已得到很好的表征，而C1和C3则通过X射线衍射进一步表征。对杂芳烃的直接CH键芳构化筛选了预催化剂的催化性能。二齿N，N-钯络合物C3与两个主链和ñ -芳基膨松性被发现是在有氧条件下高效率的预催化剂。钯负载量低至0.5-0.1 mol％，各种具有挑战性的庞大的空间芳基溴化物和杂芳基溴化物的杂芳烃都适用于这种交叉偶联反应。

  DOI：

  10.1039/c6dt02544g

文献信息

• Bulky α-diimine palladium complexes: highly efficient for direct C–H bond arylation of heteroarenes under aerobic conditions
  作者：Jia-Sheng Ouyang、Yan-Fang Li、Dong-Sheng Shen、Zhuofeng Ke、Feng-Shou Liu

  DOI：10.1039/c6dt02544g

  日期：——

  bidentate N,N-palladium complex C3 with both a backbone and N-aryl bulkiness was found to be a highly efficient precatalyst under aerobic conditions. With a low palladium loading of 0.5–0.1 mol%, a variety of heteroarenes with challenging bulky steric aryl bromides as well as heteroaryl bromides are all applicable for this cross-coupling reaction.

  通过增强主链和N-芳基部分的体积的策略，我们设计并合成了一种体积较大的α-二亚胺钯配合物（即[Ar–N C（R）–C（R）N– Ar] PdCl 2，（Ar ＝ 2-苯甲酰基-4，6-二甲基苯基）}，C1，R ＝ H；C2，R ＝ An；C3，R ＝ Ph）。这些钯配合物的结构已得到很好的表征，而C1和C3则通过X射线衍射进一步表征。对杂芳烃的直接CH键芳构化筛选了预催化剂的催化性能。二齿N，N-钯络合物C3与两个主链和ñ -芳基膨松性被发现是在有氧条件下高效率的预催化剂。钯负载量低至0.5-0.1 mol％，各种具有挑战性的庞大的空间芳基溴化物和杂芳基溴化物的杂芳烃都适用于这种交叉偶联反应。
• Establishment of Broadly Applicable Reaction Conditions for the Palladium-Catalyzed Direct Arylation of Heteroatom-Containing Aromatic Compounds
  作者：Benoît Liégault、David Lapointe、Laurence Caron、Anna Vlassova、Keith Fagnou

  DOI：10.1021/jo8026565

  日期：2009.3.6

  Conditions for the palladium-catalyzed direct arylation of a wide range of heterocycles with aryl bromides are reported. Those conditions employ a stoichiometric ratio of both coupling partners, as well as a substoichiometric quantity of pivalic acid, which results in significantly faster reactions. An evaluation of the influence of the nature of the aryl halide has also been carried out.

  报道了各种杂环与芳基溴化物进行钯催化的直接芳基化的条件。这些条件使用了两个偶联配偶体的化学计量比以及新戊酸的亚化学计量量，这导致反应明显加快。还已经进行了对芳基卤化物的性质的影响的评估。
• Direct C-H bond (Hetero)arylation of thiazole derivatives at 5-position catalyzed by N-heterocyclic carbene palladium complexes at low catalyst loadings under aerobic conditions
  作者：Bei-Bei Ma、Xiao-Bing Lan、Dong-Sheng Shen、Feng-Shou Liu、Chang Xu

  DOI：10.1016/j.jorganchem.2019.06.016

  日期：2019.10

  synthesis of 5-(hetero)arylated thiazole derivatives via an N-heterocyclic carbene palladium (Pd-NHC) complex catalyzed direct C-H arylation reaction. Utilization of this methodology, the arylation of substituted thiazoles with (hetero)aryl bromides efficiently proceeded at low catalyst loading (0.1–0.05 mol%) and under aerobic conditions. A variety of (hetero)aryl bromides, even some strongly deactivated

  已经开发了一种高效且实用的方案，用于通过N-杂环卡宾钯（Pd-NHC）络合物催化的直接CH芳基化反应合成5-（杂）芳基噻唑衍生物。利用这种方法，在低催化剂负载量（0.1–0.05 mol％）和好氧条件下，取代的噻唑与（杂）芳基溴化物的芳基化反应有效进行。在最佳反应条件下，各种具有广泛官能团的（杂）芳基溴化物，甚至一些高度失活或高度拥挤的（杂）芳基溴化物均相容。在所有情况下，目标产品的产量均中等至定量。
• A Robust and Efficient Catalyst Possessing an Electron-Deficient Ligand for the Palladium-Catalyzed Direct Arylation of Heteroarenes
  作者：Alexandra Jakab、Zoltán Dalicsek、Tibor Soós

  DOI：10.1002/ejoc.201402586

  日期：2015.1

  The exploration of the direct arylation capacity of a unique, thermally stable, and air-stable Pd0–phosphine catalyst is reported. Besides decisively contributing to catalyst robustness, the electron-deficient trifluoromethyl-substituted triphenylphosphine ligands make the palladium center more electron-deficient and accelerate the direct arylation step. The combination of only 0.5–2 mol-% of the catalyst

  报道了对独特的、热稳定的和空气稳定的 Pd0-膦催化剂的直接芳基化能力的探索。除了决定性地提高催化剂的稳定性外，缺电子的三氟甲基取代的三苯基膦配体使钯中心更加缺电子并加速直接芳基化步骤。仅 0.5-2 mol% 的催化剂和亚化学计量数量的新戊酸的组合产生了一个有效的系统，以促进广泛的电子变化的芴和芳基溴化物的联芳形成反应。观察到的区域选择性芳基化表明，C-H 活化步骤涉及协同的金属化-去质子化途径。
• Aerobic and Efficient Direct Arylation of Five-Membered Heteroarenes and Their Benzocondensed Derivatives with Aryl Bromides by Bulky α-Hydroxyimine Palladium Complexes
  作者：Bao-Tian Luo、Huan Liu、Zhi-Jie Lin、Jingxing Jiang、Dong-Sheng Shen、Rui-Zhi Liu、Zhuofeng Ke、Feng-Shou Liu

  DOI：10.1021/acs.organomet.5b00181

  日期：2015.10.26

  In the present work, a series of alpha-hydroxyimine palladium complexes with bulky substituents (i.e., [Ar-N=C(R)-C(R)(2)-OH]PdCl2} (C1, R = Me, Ar = 2-diphenylmethyl-4,6-dimethylphenyl; C2, R = Me, Ar = 2,6-bis(diphenylmethyl)-4-methylphenyl; C3, R = Me, Ar = 2,6-bis(diphenylinethyl)-4-methyoxylphenyl; C4, R = Me, Ar = 2,6-bis(diphenylmethyl)-4-chlorophenyl; C5, R = Ph, Ar = 2,6-dimethylphenyl; C6, R = Ph, Ar = 2,6-diisopropylphenyl)) were synthesized and characterized. The structures of palladium complexes C1 and C2 were determined by X-ray diffraction. These bidentate N,O-palladium complexes were applied for direct arylation under aerobic conditions. The effects of the reaction conditions and ligand substitution on the catalytic activity were evaluated. Upon a low palladium loading of 0.5 mol %, the bulky palladium complex C6 was successfully used to catalyze the cross-coupling of a variety of five-membered heteroarenes and their benzo-condensed derivatives with (hetero)aryl bromides. The mechanistic investigation on the direct arylation supported the involvement of a Pd(0)/Pd(II) CMD process.