1,3-dimesityl-5,5-dimethyl-3,4,5,6-tetrahydropyrimidin-1-ium tetrafluoroborate | 763140-20-1

• 英文名称: 1,3-dimesityl-5,5-dimethyl-3,4,5,6-tetrahydropyrimidin-1-ium tetrafluoroborate
• CAS: 763140-20-1
• 化学式: BF₄*C₂₄H₃₃N₂
• 分子量: 436.344
• InChiKey: KVYWSDYNGRTLLH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  1,3-dimesityl-5,5-dimethyl-3,4,5,6-tetrahydropyrimidin-1-ium tetrafluoroborate 在 sodium hexamethyldisilazane 作用下， 反应 1.0h， 生成
  参考文献：
  名称：

  Tuning the Electronic Properties of Carbenes: A Systematic Comparison of Neighboring Amino versus Amido Groups

  摘要：

  A related series of six-membered carbenes featuring adjoining amino and/or amido groups (i.e, a diaminocarbene, a monoamido-aminocarbene (3), and a a diamidocarbene (6)) were systematically compared using crystallographic, spectroscopic, electro-chemical, and density functional theory methods. The solid-state structure of 3 was found to exhibit inequivalent nitrogen carbon bond lengths (C-carbene-N-amide= 1.395(4) angstrom vs C-carbene-N-amine = 1.323(4) angstrom). Moreover, the C-carbene-N-amide distance was longer than that measured in the solid-state structure of 6 (1.371(3) angstrom), while the C-carbene-N-amine distance was similar to that measured in the solid-state structure of a cyclic alkyl-aminocarbene (1.315(3) angstrom). Iridium complexes of the aforementioned carbenes were also evaluated, and the collected data revealed that the introduction of carbonyl groups to the carbene-containing scaffold had a nearly linear, additive effect on the E-1/2 potential of the carbene-ligated iridium I/II redox couple (+165 mV per carbonyl added) as well as the Tolman electronic parameter value of the corresponding carbene-Ir(CO)(2)Cl complex (ca. 7 cm(-1) per carbonyl added). Beyond attenuated ligand donicity, the introduction of carbonyl groups was found to broaden the chemical reactivity: unlike prototypical N-heterocyclic carbenes, including diaminocarbenes, the monoamido-aminocarbene was found to couple to isonitriles to form the respective ketenimines.

  DOI：

  10.1021/om3001586
• 作为产物：
  描述：

  二甲基丙二酰二氯 在 吡啶 、 ammonium tetrafluoroborate 、 dimethyl sulfide borane 作用下， 以 四氢呋喃 、 正庚烷 、 二氯甲烷 为溶剂， 反应 26.0h， 生成 1,3-dimesityl-5,5-dimethyl-3,4,5,6-tetrahydropyrimidin-1-ium tetrafluoroborate
  参考文献：
  名称：

  Tuning the Electronic Properties of Carbenes: A Systematic Comparison of Neighboring Amino versus Amido Groups

  摘要：

  A related series of six-membered carbenes featuring adjoining amino and/or amido groups (i.e, a diaminocarbene, a monoamido-aminocarbene (3), and a a diamidocarbene (6)) were systematically compared using crystallographic, spectroscopic, electro-chemical, and density functional theory methods. The solid-state structure of 3 was found to exhibit inequivalent nitrogen carbon bond lengths (C-carbene-N-amide= 1.395(4) angstrom vs C-carbene-N-amine = 1.323(4) angstrom). Moreover, the C-carbene-N-amide distance was longer than that measured in the solid-state structure of 6 (1.371(3) angstrom), while the C-carbene-N-amine distance was similar to that measured in the solid-state structure of a cyclic alkyl-aminocarbene (1.315(3) angstrom). Iridium complexes of the aforementioned carbenes were also evaluated, and the collected data revealed that the introduction of carbonyl groups to the carbene-containing scaffold had a nearly linear, additive effect on the E-1/2 potential of the carbene-ligated iridium I/II redox couple (+165 mV per carbonyl added) as well as the Tolman electronic parameter value of the corresponding carbene-Ir(CO)(2)Cl complex (ca. 7 cm(-1) per carbonyl added). Beyond attenuated ligand donicity, the introduction of carbonyl groups was found to broaden the chemical reactivity: unlike prototypical N-heterocyclic carbenes, including diaminocarbenes, the monoamido-aminocarbene was found to couple to isonitriles to form the respective ketenimines.

  DOI：

  10.1021/om3001586

文献信息

• A New Ruthenium-Based Olefin Metathesis Catalyst Coordinated with 1,3-Dimesityl-1,4,5,6-tetrahydropyrimidin-2-ylidene:  Synthesis, X-ray Structure, and Reactivity
  作者：Jaesook Yun、Eric R. Marinez、Robert H. Grubbs

  DOI：10.1021/om034369j

  日期：2004.8.1

  The new ruthenium olefin metathesis catalyst 4 bearing a 5,5‘-dimethyl-1,3-dimesityl-1,4,5,6-tetrahydropyrimidin-2-ylidene ligand was first synthesized from (PCy3)2(Cl)2RuCHPh (1). The X-ray crystal structure of complex 4 has been determined and shows that the N-mesityl group of the six-membered carbene ligand and the benzylidene moiety are in close proximity (2.9 Å). This catalyst demonstrates moderate

  首先由（PCy 3）2（Cl）2 Ru合成具有5,5'-二甲基-1,3-dimesityl-1,4,5,6-四氢嘧啶-2-亚烷基配体的新型钌烯烃复分解催化剂4。 CHPh（1）。配合物4的X射线晶体结构已经确定，表明六元卡宾配体的N-甲磺酰基和亚苄基部分非常接近（2.9）。该催化剂对于闭环烯烃复分解和开环复分解聚合均显示出适度的反应性。