1-benzylidene-4,4-dimethyl-3-oxopyrazolidin-1-ium-2-ide | 606123-85-7

• 英文名称: 1-benzylidene-4,4-dimethyl-3-oxopyrazolidin-1-ium-2-ide
• 英文别名: 2-benzylidene-4,4-dimethyl-5-oxo-pyrazolidinium-1-ide
• CAS: 606123-85-7
• 化学式: C₁₂H₁₄N₂O
• 分子量: 202.256
• InChiKey: GFGFLGBJDVPYNJ-UHFFFAOYSA-N

计算性质

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

反应信息

• 作为反应物：
  描述：

  2-(三甲基硅甲基)烯丙基乙酸酯 、 1-benzylidene-4,4-dimethyl-3-oxopyrazolidin-1-ium-2-ide 在 四(三苯基膦)钯 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以94%的产率得到2,2-Dimethyl-6-methylidene-8-phenyl-1,5,7,8-tetrahydropyrazolo[1,2-a]pyridazin-3-one
  参考文献：
  名称：

  三亚甲基甲烷与偶氮甲碱亚胺的钯催化 [3 + 3] 环加成反应

  摘要：

  已开发出钯催化的三亚甲基甲烷 (TMM) 与偶氮甲亚胺的 [3 + 3] 环加成反应，以在简单和温和的条件下生产六氢哒嗪衍生物。使用取代的 TMM 前体突出了该系统与先前报道的在钯催化下 TMM 的 [3 + 2] 环加成的差异。本[3+3]环加成反应也适用于与硝酮的偶联。

  DOI：

  10.1021/ja061662c
• 作为产物：
  描述：

  氯代特戊酰氯 在 三乙胺 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 43.25h， 生成 1-benzylidene-4,4-dimethyl-3-oxopyrazolidin-1-ium-2-ide
  参考文献：
  名称：

  A New Copper-Catalyzed [3 + 2] Cycloaddition:  Enantioselective Coupling of Terminal Alkynes with Azomethine Imines To Generate Five-Membered Nitrogen Heterocycles

  摘要：

  A copper-catalyzed method for the regioselective 1,3-dipolar cycloaddition of azomethine imines to terminal alkynes has been developed. Through the use of a chiral phosphaferrocene-oxazoline ligand, a wide range of substrates can be coupled to generate useful heterocycles in very good enantiomeric excess.

  DOI：

  10.1021/ja036922u

文献信息

• Catalytic Enantioselective Trifluoromethylation of Azomethine Imines with Trimethyl(trifluoromethyl)silane
  作者：Hiroyuki Kawai、Akihiro Kusuda、Shuichi Nakamura、Motoo Shiro、Norio Shibata

  DOI：10.1002/anie.200902457

  日期：——

  It′s a cinch! The title reaction with azomethine imines 1 uses an operationally simple procedure, based on the combination of the bromide salt of cinchona alkaloids (3) and KOH. The procedure is reliable and general. Trifluoromethyl‐substituted amines can be accessed by a two‐step deprotection of the product (S)‐2.

  c！基于金鸡纳生物碱（3）的溴化物盐和KOH的组合，使用偶氮甲亚胺1的标题反应使用操作简单的程序。该程序是可靠且通用的。可通过产品（S）-2的两步脱保护来获得三氟甲基取代的胺。
• Asymmetric 1,3-Dipolar Cycloaddition Reactions of Azomethine Imines with Acrolein Catalyzed by L-Proline and Its Derivatives
  作者：Hiroyuki Suga、Tadashi Arikawa、Kennosuke Itoh、Yukihisa Okumura、Akikazu Kakehi、Motoo Shiro

  DOI：10.3987/com-10-11967

  日期：——

  cycloadditions between acrolein and various N,N'-cyclic azomethine imines in the presence of L-proline and its derivatives as organocatalysts were investigated. Reactions that were catalyzed by (S)-indline-2-carboxylic acid (30 mol%) in CHCl 3 /MeOH 97:3 (v/v) showed high exo-selectivities (exo/endo 91:9 ∼ 99:1) and enantioselectivities (75 ∼ 98% ee). In contrast, reactions catalyzed by L-proline (30

  研究了在 L-脯氨酸及其衍生物作为有机催化剂存在下丙烯醛与各种 N,N'-环偶氮甲碱亚胺之间的 1,3-偶极环加成反应。在 CHCl 3 /MeOH 97:3 (v/v) 中由 (S)-indline-2-羧酸 (30 mol%) 催化的反应显示出高外选择性（外/内 91:9 ∼ 99:1）和对映选择性（75 ∼ 98% ee）。相比之下，L-脯氨酸（30 mol%）在相似条件下催化的反​​应有利于内环加合物（83:27 ~ 99:1），对映选择性适中至良好（31 ~ 83% ee）。根据我们的研究，发现 L-脯氨酸催化反应的非对映选择性机制涉及在 L-脯氨酸存在下将外环异构化为内环加合物。
• Synthesis of pyrazolotetrazepin-7-ones from 1,3,5-triazinanes with N,N′-cyclic azomethine imines via a formal (5 + 2) pathway
  作者：Bin Cheng、Yixuan He、Hongjian Yang、Hui Li、Xinping Zhang、Wei Xu、Haiyan Sun、Taimin Wang、Hongbin Zhai

  DOI：10.1016/j.tet.2021.132130

  日期：2021.6

  The synthesis of pyrazolotetrazepin-7-ones from 1,3,5-triazinanes with N,N′-cyclic azomethine imines was achieved via a formal (5 + 2) pathway under thermal conditions. The annulation reaction is catalyst-free and additive-free.

  由 1,3,5-三嗪烷与 N,N'-环状偶氮甲亚胺合成 pyrazolotetrazepin-7-ones 是通过正式的 (5 + 2) 途径在热条件下实现的。环化反应是无催化剂和无添加剂的。
• Diastereo‐ and Enantioselective Silver‐Catalyzed [3+3] Cycloaddition and Kinetic Resolution of Azomethine Imines with Activated Isocyanides
  作者：Ling‐Fei Tao、Sen Zhang、Fen Huang、Wen‐Tao Wang、Zhang‐Hong Luo、Linghui Qian、Jia‐Yu Liao

  DOI：10.1002/anie.202202679

  日期：2022.6.7

  diastereo- and enantioselective [3+3] cycloaddition of activated isocyanides with azomethine imines is reported for the first time. Under silver catalysis, a series of bicyclic 1,2,4-triazines were obtained in high yields with high stereoselectivities. The versatility of this system was further demonstrated by the late-stage functionalization of complex bioactive molecules and the kinetic resolution of racemic

  首次报道了活化异氰化物与偶氮甲碱亚胺的前所未有的非对映和对映选择性 [3+3] 环加成反应。在银催化下，以高收率和高立体选择性获得了一系列双环1,2,4-三嗪。复杂生物活性分子的后期功能化和外消旋甲亚胺的动力学拆分进一步证明了该系统的多功能性。
• Highly Diastereoselective DABCO-Catalyzed [3 + 3]-Cycloaddition of 1,4-Dithiane-2,5-diol with Azomethine Imines
  作者：Xin Fang、Jun Li、Hai-Yan Tao、Chun-Jiang Wang

  DOI：10.1021/ol402724h

  日期：2013.11

  An effective diastereoselective [3 + 3] cycloaddition of 1,4-dithiane-2,5-diol with azomethine imines catalyzed by DABCO is described. A variety of highly functionalized six-membered dinitrogen-fused heterocycles can be obtained in good yield with excellent diastereoselectivity, which was controlled by anomeric effect.