dimethyl 3-(dimethylamino)-1,4-dimethyl-5H-cyclopenta[c]-pyridine-6,6(7H)-dicarboxylate | 1323947-48-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: dimethyl 3-(dimethylamino)-1,4-dimethyl-5H-cyclopenta[c]-pyridine-6,6(7H)-dicarboxylate
• 英文别名: dimethyl 3-(dimethylamino)-1,4-dimethyl-5H-cyclopenta[c]pyridine-6,6(7H)-dicarboxylate；dimethyl 3-(dimethylamino)-1,4-dimethyl-5H,7H-cyclopenta[c]pyridine-6,6-dicarboxylate；Dimethyl 3-(dimethylamino)-1,4-dimethyl-5,7-dihydrocyclopenta[c]pyridine-6,6-dicarboxylate
• CAS: 1323947-48-3
• 化学式: C₁₆H₂₂N₂O₄
• 分子量: 306.362
• InChiKey: PGBLOHFZCFUGJX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  68.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  dimethyl 2,2-di(but-2-yn-1-yl)malonate 、 二甲基氢胺 在 [Ni(IPr)]₂ 作用下， 以 氘代甲苯 为溶剂， 生成 dimethyl 3-(dimethylamino)-1,4-dimethyl-5H-cyclopenta[c]-pyridine-6,6(7H)-dicarboxylate
  参考文献：
  名称：

  Ni(IPr)2 催化的炔烃和腈环加成生成吡啶的机理评价：形成关键 η1-Ni(IPr)2(RCN) 中间体的证据

  摘要：

  对 Ni(IPr) 2催化的二炔和腈的 [2 + 2 + 2] 环加成进行了详细的机理评估。通过对这些反应的动力学分析、观察到的产物区域选择性和化学计量反应，与其他常见的环加成催化剂相比，Ni(IPr) 2催化的二炔和腈的环加成似​​乎是通过杂氧化偶联机制进行的。反应曲线显示出对腈的强烈依赖性，导致可变的腈依赖性静息状态。卡宾配体的强配位和相当大的空间体积有利于腈的选择性初始结合，从而形成异偶联途径。原位 IR 数据表明腈的初始结合位于罕见的 η 1结合构象。腈配位之后是腈的速率决定性触觉变化和随后的卡宾损失。炔烃配位然后导致杂氧化偶联、侧链炔烃的插入和还原消除以提供吡啶产物。

  DOI：

  10.1021/om400666k

文献信息

• Nickel-Catalyzed [2+2+2] Cycloaddition of Diynes and Cyanamides
  作者：Ryan M. Stolley、Michael T. Maczka、Janis Louie

  DOI：10.1002/ejoc.201100428

  日期：2011.7

  A variety of bicyclic N,N-disubstituted 2-aminopyridines have been prepared from diynes and cyanamides by nickel-catalyzed [2+2+2] cycloaddition reactions. The reactions proceeded at room temperature with low catalyst loading to afford 2-aminopyridines in good to excellent yields. The method is amenable to both internal and terminal diynes and proceeds in a regioselective manner. A number of cyanamides

  通过镍催化的[2+2+2]环加成反应，由二炔和氰胺制备了多种双环N,N-二取代2-氨基吡啶。该反应在室温下以低催化剂负载量进行，以良好至优异的收率提供2-氨基吡啶。该方法适用于内部二炔和末端二炔，并以区域选择性方式进行。使用了许多具有不同官能团耐受性的氰胺。使用3-己炔和N-氰基吡咯烷的分子间形式也以良好的收率提供了所需的N,N-二取代的2-氨基吡啶。
• Iron-Catalyzed Cycloaddition Reaction of Diynes and Cyanamides at Room Temperature
  作者：Chunxiang Wang、Dongping Wang、Fen Xu、Bin Pan、Boshun Wan

  DOI：10.1021/jo400057t

  日期：2013.4.5

  An iron-catalyzed [2 + 2 + 2] cycloaddition reaction of diynes and cyanamides at room temperature is reported. Highly substituted 2-aminopyridines were obtained in good to excellent yields with high regioselectivity. Insights toward the reaction process were investigated through in situ IR spectra and control experiments. In this iron-catalyzed cycloaddition reaction, the active iron species was generated only in the presence of both alkynes and nitriles. The lower reaction temperature, broad substrates scope, and inversed regioselectivity make it a complementary method to the previously developed iron catalytic system.
• Iron-Catalyzed Formation of 2-Aminopyridines from Diynes and Cyanamides
  作者：Timothy K. Lane、Brendan R. D’Souza、Janis Louie

  DOI：10.1021/jo3012418

  日期：2012.9.7

  Diynes and cyanamides undergo an iron-catalyzed [2 + 2 + 2] cycloaddition to form highly substituted 2-aminopyridines in an atom-efficient manner that is both high yielding and regioselective. This system was also used to cyclize two terminal alkynes and a cyanamide to afford a 2,4,6-trisubstituted pyridine product regioselectively.