2-(3-oxopyrazolidin-1-yl)-2-phenylacetonitrile | 1427576-91-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 2-(3-oxopyrazolidin-1-yl)-2-phenylacetonitrile
• 英文别名: (2S)-2-(3-oxopyrazolidin-1-yl)-2-phenylacetonitrile
• CAS: 1427576-91-7
• 化学式: C₁₁H₁₁N₃O
• 分子量: 201.228
• InChiKey: JQZSZQSGVDGDBS-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  56.1
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  三甲基氰硅烷 、 1-benzylidene-3-oxo-1-pyrazolidinium-2-ide 在 1-((1S,2R)-2-hydroxy-1,2-diphenylethyl)-3-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)thiourea 作用下， 以 均三甲苯 为溶剂， 反应 18.0h， 以97%的产率得到2-(3-oxopyrazolidin-1-yl)-2-phenylacetonitrile
  参考文献：
  名称：

  Enantioselective Strecker-type reaction between azomethine imines and trimethylsilyl cyanide catalyzed by a cinchona alkaloid-derived thiourea bearing multiple hydrogen-bonding donors

  摘要：

  不对称的斯特克反应在氮杂烯咪唑和TMSCN之间进行，催化剂为1摩尔%的源自金鸡纳碱的多氢键供体的硫脲，最终以良好至优异的收率和对映选择性合成了光学活性的氨基腈。

  DOI：

  10.1039/c3ra41640b

文献信息

• Multiple Hydrogen‐Bonding Catalysts Enhance the Asymmetric Cyanation of Ketimines and Aldimines
  作者：Yunhui Zhao、Yueyang Luo、Jun Liu、Changwu Zheng、Gang Zhao

  DOI：10.1002/chem.202302061

  日期：2023.10.9

  A highly enantioselective cyanation of imines (up to >99 % ee) has been developed using well-designed C2-symmetric hydrogen bonding catalysts. This catalytic system is distinguished by its low catalyst loading (S/C up to 1000), high efficiency, extremely broad substrate scope, scalability and mild reaction conditions.

  使用精心设计的 C 2对称氢键催化剂开发了亚胺的高度对映选择性氰化（高达 >99 % ee）。该催化体系的特点是催化剂负载量低（S/C高达1000）、效率高、底物范围极广、可扩展性和反应条件温和。
• Chiral Iron(II) NPPN Complexes: Synthesis and Application in the Asymmetric Strecker Reaction of Azomethine Imines
  作者：Raffael Huber、Raphael Bigler、Antonio Mezzetti

  DOI：10.1021/acs.organomet.5b00357

  日期：2015.7.13

  The open-chain NPPN ligand (1S,1'S)-1,1'-((ethane-1,2-diylbis(phenylphosphanediyl))bis(2,1-phenylene))bis(N-cyclohexylmethanimine) (1) was prepared by condensation of cyclohexylamine with enantiomerically pure (1S,1'S)-2,2'-(ethane-1,2-diylbis(phenylphosphanediyl))dibenzaldehyde ((S,S)-6). Ligand 1 coordinates to [Fe(OH2)(6)](BF4)(2) or [Fe(MeCN)(6)](SbF6)(2) in acetonitrile to give the dicationic complex [Fe(MeCN)(2)(1)](X)(2) (2) (X = BF4 or SbF6). The corresponding carbonyl (3), bromocarbonyl (4), and bis(tert-butylisonitrile) (5) derivatives were prepared and fully characterized. Complex 2 reacts with Me3SiCN to give the corresponding trimethylsilyl isocyanide derivative 18 featuring a Fe-CNSiMe3 linkage. The X-ray structures of 2, 3, 5, and 18 show that ligand 1 assumes the Lambda-cis-alpha geometry, which allows comparing the trans influence of these ligands. Complexes 2, 3, 5, and 18 were applied in the asymmetric addition of trimethylsilyl cyanide to azomethine imines (Strecker reaction), whose enantioselectivity reached 22% ee. The low enantioselectivity can be explained on the basis of the Me3SiCN/Me3SiNC isomerization and of the reaction product partially displacing the NPPN ligand from iron.