(Z)-4,4-dimethyl-5-(pyridin-3-ylmethylene)-1,3-dioxolan-2-one | 1448750-37-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (Z)-4,4-dimethyl-5-(pyridin-3-ylmethylene)-1,3-dioxolan-2-one
• 英文别名: (5Z)-4,4-dimethyl-5-(pyridin-3-ylmethylidene)-1,3-dioxolan-2-one
• CAS: 1448750-37-5
• 化学式: C₁₁H₁₁NO₃
• 分子量: 205.213
• InChiKey: VMYQAZVNQDQCAR-TWGQIWQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  48.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-methyl-4-(pyridin-3-yl)but-3-yn-2-ol 、 二氧化碳 在 C₉H₁₄N₂O₂ 作用下， 以 neat (no solvent) 为溶剂， 60.0 ℃ 、2.0 MPa 条件下， 反应 2.0h， 以96%的产率得到(Z)-4,4-dimethyl-5-(pyridin-3-ylmethylene)-1,3-dioxolan-2-one
  参考文献：
  名称：

  极化烯烃的可分离CO2加合物：高热稳定性和CO2化学转化的催化活性

  摘要：

  首先合成了从市售的1，5-二氮杂双环[4.3.0] non-5-烯（DBN）衍生而来的四氢嘧啶-2-亚烷基（THPE）的各种CO 2加合物。X射线单晶分析表明，对于THPE-CO 2加合物，结合的CO 2的弯曲几何结构的O-C-O角为127.50-129.51° 。原位FTIR实验表明，THPE-CO 2加合物在DMSO中具有前所未有的热稳定性，即使在100°C时也不会分解。发现THPE-CO 2加合物在催化CO 2的羧基环化反应中具有很高的活性。在温和条件下使用炔丙醇，明显高于先前报道的有机催化剂。在这些过程中可以耐受各种内部和末端官能化的炔丙醇，以中等至良好的产率提供相应的α-亚烷基环状碳酸酯，并具有完全的（Z）-立体选择性。同位素标记与原位FTIR和化学计量学实验相结合，表明催化反应倾向于通过THPE-CO 2介导的碱性离子对机理进行。

  DOI：

  10.1002/adsc.201801194

文献信息

• Fast CO₂ Sequestration, Activation, and Catalytic Transformation Using <i>N</i>-Heterocyclic Olefins
  作者：Yan-Bo Wang、Yi-Ming Wang、Wen-Zhen Zhang、Xiao-Bing Lu

  DOI：10.1021/ja405114e

  日期：2013.8.14

  N-Heterocyclic Olefin (NHO) with high electronegativity at the terminal carbon atom was found to show a strong tendency for CO2 sequestration, affording a CO2 adduct (NHO-CO2). X-ray single crystal analysis revealed the bent geometry of the binding CO2 in the NHO-CO2 adducts with an O-C-O angle of 127.7-129.9 degrees, dependent on the substitute groups of N-heterocyclic ring. The length of the C-carboxylate-C-NHO bond is in the range of 1.55-1.57 angstrom, significantly longer than that of the C-carboxylate-C-NHC bond (1.52-1.53 angstrom) of the previously reported NHC-CO2 adducts. The FTIR study by monitoring the v(CO2) region of transmittance change demonstrated that the decarboxylation of NHO-CO2 adducts is easier than that of the corresponding NHC-CO2 adducts. Notably, the NHO-CO2 adducts were found to be highly active in catalyzing the carboxylative cyclization of CO2 and propargylic alcohols at mild conditions (even at ambient temperature and 0.1 MPa CO2 pressure), selectively giving alpha-alkylidene cyclic carbonates in good yields. The catalytic activity is about 10-200 times that of the corresponding NHC-CO2 adducts at the same conditions. Two reaction paths regarding the hydrogen at the alkenyl position of cyclic carbonates coming from substrate (path A) or both substrate and catalyst (path B) were proposed on the basis of deuterium labeling experiments. The high activity of NHO-CO2 adduct was tentatively ascribed to its low stability for easily releasing the CO2 moiety and/or the desired product, a possible rate-limiting step in the catalytic cycle.