1,3-dimesityl-5-methyl-6-oxo-6H-pyrimidinium-4-olate | 1051375-11-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 1,3-dimesityl-5-methyl-6-oxo-6H-pyrimidinium-4-olate
• CAS: 1051375-11-1
• 化学式: C₂₃H₂₆N₂O₂
• 分子量: 362.472
• InChiKey: STNZGZBUVJSCDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.35
• 重原子数：
  27.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 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-methyl-6-oxo-6H-pyrimidinium-4-olate 在 正丁基锂 、 selenium 、 盐酸 作用下， 以 四氢呋喃 、 正己烷 、 乙醚 为溶剂， 反应 3.25h， 以69%的产率得到1,3-dimesityl-5-methyl-2-selenoxohexahydropyrimidin-4,6-dione
  参考文献：
  名称：

  阴离子和中性丙二酸衍生的 N-杂环卡宾的 π 酸度的实验评估

  摘要：

  阴离子丙二酸衍生的 N-杂环卡宾 (maloNHC)¯, [1]¯ 的 π 酸度已通过记录相应 maloNHC∙Se 加合物的 77Se NMR 化学位移实验确定。尽管本质上是阴离子，[1]¯ 显示出显着的 π 接受特性，可以根据反阳离子的性质对其进行微调。中性maloNHC衍生的卡宾的π酸度也通过丙二酸主链的中和进行评估，并显示在O-甲基化时增加，产生（氨基）（丙烯酰胺）卡宾1Me，并在质子化时增加更多的中心碳原子，正式生成二酰氨基卡宾 1H。

  DOI：

  10.1002/ejic.201700883
• 作为产物：
  描述：

  N,N'-dimesitylformamidine 、 甲基丙二酸 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89%的产率得到1,3-dimesityl-5-methyl-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

• Anionic and zwitterionic copper(i) complexes incorporating an anionic N-heterocyclic carbene decorated with a malonate backbone: synthesis, structure and catalytic applications
  作者：Vincent César、Cécile Barthes、Yoann C. Farré、Stéphane V. Cuisiat、Bernard Y. Vacher、Rémy Brousses、Noël Lugan、Guy Lavigne

  DOI：10.1039/c3dt32919d

  日期：——

  The anionic malonate-derived N-heterocyclic carbenes (maloNHCs) react cleanly and rapidly with copper chloride to generate the anionic complexes of type [(maloNHC)CuCl]·Li, which crystallize in the solid state either in an oligomeric trimer arrangement or in polymeric helixes depending on the substitution pattern and the solvent. Ten zwitterionic heteroleptic Cu(I) complexes combining the anionic maloNHC

  阴离子丙二酸酯衍生的N-杂环卡宾（malo NHCs）与氯化铜生成[（马洛NHC）CuCl]·Li型阴离子配合物，根据取代方式和溶剂的不同，它们以低聚三聚体排列或聚合螺旋的形式固态结晶。还以非常选择性的方式获得了十种两性离子杂合Cu（I）络合物，该络合物结合了阴离子苹果醇NHC和中性咪唑-2-亚烷基，并进行了充分表征。尽管阴离子络合物是羰基化合物氢化硅烷化的相对活性催化剂，但两性离子络合物对于重氮酯的分子内环丙烷化反应却是高效且非常耐用的预催化剂，其性能优于相应的阳离子Cu（I）与经典的咪唑-2-亚基络合物。
• The Ambivalent Chemistry of a Free Anionic N-Heterocyclic Carbene Decorated with a Malonate Backbone: The Plus of a Negative Charge
  作者：Vincent César、Stéphane Labat、Karinne Miqueu、Jean-Marc Sotiropoulos、Rémy Brousses、Noël Lugan、Guy Lavigne

  DOI：10.1002/chem.201303184

  日期：2013.12.9

  family of N‐heterocyclic carbenes incorporating an anionic backbone; here, a malonate group. A comprehensive experimental exploration of its chemistry as a free entity (in the form of its lithium salt [1]⋅Li) is presented, and rationalized using DFT calculations at the B3LYP/6‐31+G** level of theory. For the sake of comparison, similar computations were performed on other representative carbene types.

  阴离子杂环“ [ Malo NHC] - ”（[ 1 ] -）是结合阴离子主链的N-杂环卡宾族生长家族的原型。在这里，一个丙二酸集团。提出了对其作为游离实体的化学形式（以其锂盐[ 1 ] ⋅Li的形式）进行的全面实验探索，并在理论水平B3LYP / 6-31 + G **下使用DFT计算对其进行了合理化。为了进行比较，对其他代表性的卡宾类型进行了类似的计算。[ 1 ]·Li与一系列亲电试剂的反应用于确定其固有性质，即亲核卡宾。没想到，[ 1还发现]⋅Li与亲核叔丁基异氰化物反应，得到阴离子型酮亚胺，随后可通过酮亚胺部分的质子化将其衍生为亚胺，或通过环内丙二酸酯部分的烷基化将其衍生为中性酮亚胺。 。上的亲电行为进一步实验[ 1 ]⋅Li透露了其朝向预期的反应性p氯苯甲醛，产生了正式ç  ħ激活和布瑞斯罗夫中间的第一结构表征酮互变异构体。最后，[ 1 ]⋅Li显着激活极性Ë  H键，包括N-
• Zwitterionic Mixed‐Carbene Coinage Metal Complexes: Synthesis, Structures, and Photophysical Studies
  作者：Florian Chotard、Alexander S. Romanov、David L. Hughes、Mikko Linnolahti、Manfred Bochmann

  DOI：10.1002/ejic.201900573

  日期：2019.10.31

  (3) have been synthesized, based on a combination of ethyl-substituted cyclic (alkyl)(amino)carbene (Et2CAAC) and an anionic methyl-malonate-derived N-heterocyclic carbene (maloNHC). The crystal structures confirm the linear two-coordinate geometry without close intermolecular contacts. The compounds show blue-white phosphorescence consistent with a wide HOMO-LUMO energy gap (2.87–3.07 eV) estimated

  基于乙基取代的环状（烷基）（氨基）卡宾（Et2CAAC）的组合，已经合成了一系列铜（1）、银（2）和金（3）的三种两性离子混合配体双（卡宾）配合物) 和阴离子甲基丙二酸酯衍生的 N-杂环卡宾 (maloNHC)。晶体结构证实了线性双坐标几何结构，没有紧密的分子间接触。这些化合物显示出与通过循环伏安法估计的宽 HOMO-LUMO 能隙 (2.87–3.07 eV) 一致的蓝白色磷光。结晶粉末的激发态寿命在 Cu > Ag > Au 系列中降低，从铜的 400 µs 到金配合物的 50 µs 3。DFT 计算表明激发时跃迁偶极矩发生了很大变化，高达 16 D.
• (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.
• Nickel(II) Complexes of Highly σ-Donating Cyclic (Alkyl)(Amino)- and Malonate-Carbenes: Syntheses and Catalytic Studies
  作者：Mickaël Henrion、Bernardo de P. Cardoso、Vincent César、Michael J. Chetcuti、Vincent Ritleng

  DOI：10.1021/acs.organomet.6b00906

  日期：2017.3.27

  [NiCl2(PPh3)(2)] reacted with the cyclic (alkyl)-(amino)carbene IPr-CAAC(Me2)-Cy (a) and with the anionic malonate-carbene Mes-maloNHC(Me)-Mes (b) to give the neutral and zwitterionic complexes [NiCl2(IPr-CAAC(Me2)-Cy)(PPh3)] (1a) and [NiCl(Mes-maloNHC(Me)-Mes)(PPh3)(2)] (3b), resulting from the respective substitution of one neutral triphenylphosphine (L-type) and one anionic chloride (X-type) ligand. Complex la decomposed in the presence of traces of protons to give the nickelate salt [(IPr-CAAC(Me2)-Cy)center dot H][NiCl3(PPh3)] (2a). Complex 3b was insoluble in most organic solvents and thus difficult to purify and characterize, but the propensity of b to substitute X-type ligands was further illustrated by the substitution of iodide from the N-heterocyclic carbene complex [NiICp(IMe)] to give the zwitterionic heteroleptic biscarbene complex [NiCp(IMe)(Mes-maloNHC(Me)-Mes)] (4b), which was characterized by X-ray crystallography. The latter was postfunctionalized by the addition of methyl triflate on the malonate moiety to give the corresponding cationic species [NiCp(IMe)(Mes-maloNHC(Me)(Me)-Mes)](OTf (5c), in which the ligand electron donicity is greatly reduced. Complexes 3b, 4b, and 5c are the first Ni(maloNHC) species, and la joins a very restricted list of Ni(CAAC) complexes. The catalytic activity of la, 4b, and 5c was studied in a cross-coupling reaction, a reduction reaction of a C-heteroatom double bond, and a C-H bond functionalization reaction.