N¹,N³-dimesityl-2,2-dimethylmalonamide | 763140-17-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N¹,N³-dimesityl-2,2-dimethylmalonamide
• CAS: 763140-17-6
• 化学式: C₂₃H₃₀N₂O₂
• 分子量: 366.503
• InChiKey: OHCCFNVOQDGTLB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.14
• 重原子数：
  27.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  58.2
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  N¹,N³-dimesityl-2,2-dimethylmalonamide 在 ammonium tetrafluoroborate 、 dimethyl sulfide borane 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正庚烷 为溶剂， 反应 25.0h， 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：

  2,4,6-三甲基苯胺 、 二甲基丙二酰二氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以64%的产率得到N¹,N³-dimesityl-2,2-dimethylmalonamide
  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

• Diamidocarbenes as versatile and reversible [2 + 1] cycloaddition reagents
  作者：Jonathan P. Moerdyk、Christopher W. Bielawski

  DOI：10.1038/nchem.1267

  日期：2012.4

  covalent chemistry. In addition, a diamidocyclopropane derivative prepared via this method was hydrolysed successfully to form the corresponding linear carboxylic acid in a metal- and carbon monoxide-free hydrocarboxylation reaction. As such, diamidocarbenes are expected to find utility in the synthesis of cyclopropanes, epoxides and their derivatives, as well as in dynamic covalent chemistry applications

  我们描述了通过结合易于获得且可分离的N , N 来合成各种环丙烷和环氧化物'-二氨基卡宾与一系列结构和电子不同的烯烃和醛，包括富电子衍生物。令人惊讶的是，发现环丙烷化和环氧化反应在相对较低的温度下是快速且热可逆的，这是利用动态共价化学的应用通常需要的两个特征。此外，通过该方法制备的二酰氨基环丙烷衍生物在不含金属和一氧化碳的加氢羧化反应中成功水解形成相应的线性羧酸。因此，预计二酰氨基卡宾可用于环丙烷、环氧化物及其衍生物的合成，以及动态共价化学应用。