1,3-dimesityl-5-tert-butyl-6-oxo-6H-pyrimidinium-4-olate | 1051375-14-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1,3-dimesityl-5-tert-butyl-6-oxo-6H-pyrimidinium-4-olate
• CAS: 1051375-14-4
• 化学式: C₂₆H₃₂N₂O₂
• 分子量: 404.552
• InChiKey: HIGVBRQCLJGNBL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.34
• 重原子数：
  30.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  48.94
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1,3-dimesityl-5-tert-butyl-6-oxo-6H-pyrimidinium-4-olate 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.5h， 以100%的产率得到
  参考文献：
  名称：

  金 (I) 的阴离子 N-杂环卡宾配合物作为烯炔无银环异构化的预催化剂

  摘要：

  阴离子丙二酸酯衍生的 N-杂环卡宾 maloNHC 容易且有效地与 AuCl(tht) 反应生成相应的 [(maloNHC)AuCl](M) 型阴离子金 (I) 配合物。这些配合物与三苯基膦的化学计量反应得到两性离子配合物 [(maloNHC)Au(PPh3)]。尽管完全不溶于反应介质，[(maloNHC)AuCl](M) 盐被证明是适合 1,6-烯炔环异构化的预催化剂，通过原位生成 [(maloNHC)AuCl )Au]。

  DOI：

  10.1002/ejic.201500168
• 作为产物：
  描述：

  N,N'-dimesitylformamidine 、 2-叔-丁基丙二酸 在 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以93%的产率得到1,3-dimesityl-5-tert-butyl-6-oxo-6H-pyrimidinium-4-olate
  参考文献：
  名称：

  一种稳定的阴离子N-杂环卡宾及其两性离子配合物

  摘要：

  Pyrimidinium 甜菜碱 (1) 可通过甲脒和单取代丙二酸的直接模块化合成轻松获得，很容易被 nBuLi（或 KHMDS）去质子化，得到稳定的卡宾物质 [2]Li+（缩写为 maloNHC）。后者代表了 N-杂环卡宾亚组的原型，在其杂环骨架内结合了丙二酸酯作为远程阴离子官能团。在发挥单齿 2 e-L 型供体和非配位电荷载流子 X 的双重作用的同时，此类配体被认为提供了形成两性离子复合物的合理途径，如这里通过三个例子（Rh、Fe、Ag）所示。特别是 [2]Li+ 与 [RhCl(1,

  DOI：

  10.1021/ja804296t

文献信息

• (Cyclopentadienyl)iron(II) Complexes of N-Heterocyclic Carbenes Bearing a Malonate or Imidate Backbone: Synthesis, Structure, and Catalytic Potential in Hydrosilylation
  作者：Vincent César、Luis C. Misal Castro、Thomas Dombray、Jean-Baptiste Sortais、Christophe Darcel、Stéphane Labat、Karinne Miqueu、Jean-Marc Sotiropoulos、Rémy Brousses、Noël Lugan、Guy Lavigne

  DOI：10.1021/om400625q

  日期：2013.8.26

  The backbone-functionalized anionic carbenes maloNHC (1(R); malonate backbone) and imidNHC (2; imidate backbone) were generated in situ from their respective zwitterionic precursors and treated with FeCp(CO)(2)I to afford the zwitterionic complexes FeCp(CO)(2)(1(R))} (3R; 5984% yield), and FeCp(CO)(2)(2)} (4; 77% yield), respectively. Methylation of the malonate complex 3Me takes place at one of the backbone oxygen atoms to give the cationic adduct [FeCp(CO)(2)(1MeMe)](OTf) ([5(Me)](OTf); 96% yield), whereas methylation of 4 takes place at the imidate nitrogen atom to produce the cationic adduct [FeCp(CO)(2)(2(Me))](OTf) ([6(Me)](OTf); 84% yield). All of the complexes were characterized by NMR and IR in solution, while X-ray structure analyses were carried out for 3(Me), 4, and [6(Me)](OTf). In addition, a detailed experimental and theoretical investigation of the electron density within the archetypal zwitterionic complex 3Me was carried out. The observation of short intramolecular contacts between Cipso or Cortho of the mesityl groups of the carbene and the proximal carbonyl groups is rationalized in terms of a noncovalent through space pi-pi* interaction involving a two-electron delocalization of the occupied pi(Cipso pi Cortho) molecular orbital (MO) of the aryl ring into one vacant pi*(C pi O) MO of the carbonyl ligand. A theoretical analysis carried out on dissymmetrical model complexes reveals that the magnitude of such an interaction is correlated with the donor properties of aryl group substituents. A catalyst screening of the above complexes in the hydrosilylation of benzaldehyde under visible light irradiation revealed a dramatic effect of the electronic donor properties of these carbenes on the performances of their complexes, with the more nucleophilic carbene 1tBu in the zwitterionic species 3tBu appearing as the most efficient. This complex shows good efficiency and excellent chemoselectivity in the hydrosilylation of various aldehydes bearing reactive functional groups. It is also moderately active in the hydrosilylation of a few ketone substrates and exhibits very good performance in the hydrosilylation of representative aldimines and ketimines.