1-(1-naphthylmethyl)-5,5-dimethyl-pyrazolidin-3-one | 365456-19-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-(1-naphthylmethyl)-5,5-dimethyl-pyrazolidin-3-one
• 英文别名: 5,5-dimethyl-1-(1-naphthylmethyl)-pyrazolidin-3-one；5,5-dimethyl-1-(naphthalen-1-ylmethyl)pyrazolidin-3-one
• CAS: 365456-19-5
• 化学式: C₁₆H₁₈N₂O
• 分子量: 254.332
• InChiKey: GILBDVXQSQIEHR-UHFFFAOYSA-N

物化性质

• 熔点：
  152-154 °C(Solv: hexane (110-54-3); ethyl acetate (141-78-6))
• 密度：
  1.139±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.86
• 重原子数：
  19.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  32.34
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-(1-naphthylmethyl)-5,5-dimethyl-pyrazolidin-3-one 在 copper(II) bis(trifluoromethanesulfonate) 、 lithium chloride 、 S-4,5-二氢-2-(2-((S)-4,5-二氢-4-异丙基噁唑-2-基)丙-2-基)-4-异丙基噁唑 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 benzyl (1S,4S,7S)-7-[3,3-dimethyl-2-(naphthalen-1-ylmethyl)-5-oxopyrazolidine-1-carbonyl]-2-azabicyclo[2.2.2]oct-5-ene-2-carboxylate
  参考文献：
  名称：

  Highly Enantioselective Synthesis of Isoquinuclidine by Diels-Alder Reaction of 1,2-Dihydropyridine Utilizing Chiral Bisoxazoline-Cu(II) Complex

  摘要：

  The enantioselective Diels-Alder (D-A) reaction between N-phenoxycarbonyl- or N-benzyloxycarbonyl-1,2-dihydropyridine (1a or 1b) and N(2)-acryloyl-N(1)-(1-naphthylmethyl)-5,5-dimethylpyrazolidin-3-one (2b) using (S,S)-bisoxazoline-Cu(II) catalyst (A, B, C or D) has been investigated. Utilizing (S,S)-t-Bu-bisoxazoline-Cu(II) catalyst C, the D-A reaction of la and 2 afforded the endo-(7S)-isoquinuclidines (3, 4 or 5) in good chemical yields with high enantioselectivity (up to 99% e.e.).

  DOI：

  10.3987/com-12-s(n)2
• 作为产物：
  描述：

  3-甲基-2-丁烯酸乙酯 在 potassium carbonate 、 一水合肼 、 sodium iodide 作用下， 以 乙醇 、 丁酮 为溶剂， 反应 7.0h， 生成 1-(1-naphthylmethyl)-5,5-dimethyl-pyrazolidin-3-one
  参考文献：
  名称：

  An efficient synthetic methodology of chiral isoquinuclidines by the enantioselective Diels–Alder reaction of 1,2-dihydropyridines using chiral cationic palladium–phosphinooxazolidine catalyst

  摘要：

  High purity chiral isoquinuclidines (97%ee) were obtained from the enantioselective Diels-Alder reaction of 1-phenoxycarbonyl-1,2-dihydropyridine with 1-benzyl-2-acry loylpyrazolidin-3-one using chiral cationic palladiurn-phosphinooxazolidine (Pd-POZ) catalyst. The obtained DA adduct was easily converted to the chiral piperidine derivative bearing three stereogenetic centers in the structure. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.08.099

文献信息

• Fluxional Additives:  A Second Generation Control in Enantioselective Catalysis
  作者：Mukund P. Sibi、Shankar Manyem、Hector Palencia

  DOI：10.1021/ja064472a

  日期：2006.10.1

  The concept of "fluxional additives", additives that can adopt enantiomeric conformations depending on the chiral information in the ligand, is demonstrated in enantioselective Diels-Alder and nitrone cycloaddition reactions. The additive design is modular, and diverse structures are accessible in three steps. Chiral Lewis acids from main group and transition metals show enhancements in enantioselectivity

  “通量添加剂”的概念，即可以根据配体中的手性信息采用对映体构象的添加剂，在对映选择性 Diels-Alder 和硝酮环加成反应中得到了证明。增材设计是模块化的，可以通过三个步骤访问不同的结构。在这些添加剂的存在下，来自主族和过渡金属的手性路易斯酸显示出对映选择性的增强。
• The Role of Achiral Pyrazolidinone Templates in Enantioselective Diels−Alder Reactions:  Scope, Limitations, and Conformational Insights
  作者：Mukund P. Sibi、Levi M. Stanley、Xiaoping Nie、Lakshmanan Venkatraman、Mei Liu、Craig P. Jasperse

  DOI：10.1021/ja066425o

  日期：2007.1.1

  were also observed in reactions of 7d with chiral Lewis acids derived from relatively small chiral ligands, suggesting the pyrazolidinone templates are capable of relaying stereochemical information from the ligand to the reaction center. Lewis acids capable of adapting square planar geometries, such as Cu(OTf)2, Cu(ClO4)2, and Pd(ClO4)2, were found to be particularly effective at providing high selectivities

  我们评估了非手性吡唑烷酮模板与手性路易斯酸在室温、对映选择性 Diels-Alder 环加成反应中的作用。检查了fluxional N(1) 取代基的作用，庞大的1-萘甲基组提供高达99%ee 的对映选择性，而具有较小fluxional 组的模板提供较低的选择性。在 7d 与衍生自相对较小手性配体的手性路易斯酸的反应中也观察到高选择性，表明吡唑烷酮模板能够将立体化学信息从配体传递到反应中心。发现能够适应方形平面几何形状的路易斯酸，例如 Cu(OTf)2、Cu(ClO4)2 和 Pd( )2，在提供高选择性方面特别有效。此外，已证明吡唑烷酮模板的 C-5 位取代对最佳选择性至关重要。附加有许多常见的亲二烯体和各种二烯的最佳吡唑烷酮的反应证明了这种非手性模板的实用性。此外，催化负载可以降低到 2.5 mol%，而选择性基本上没有损失。Pi-Pi 相互作用被评估为一种解释在室温下观察到的异常高选择性的手段。最后，采用非
• Chiral Lewis Acid Catalysis in Nitrile Oxide Cycloadditions
  作者：Mukund P. Sibi、Kennosuke Itoh、Craig P. Jasperse

  DOI：10.1021/ja0318636

  日期：2004.5.1

  examples of highly regio- and enantioselective nitrile oxide cycloadditions to unsaturated alkenes using substoichiometric amounts of a chiral Lewis acid. Pyrazolidinones proved to be effective achiral templates in the cycloadditions providing C-adducts typically in >30:1 selectivity and 80-99% ee. To avoid potential problems involving coordination of the Lewis acid by amine bases, we have devised a novel

  我们描述了使用亚化学计量量的手性路易斯酸对不饱和烯烃进行高度区域选择性和对映选择性氧化腈环加成的例子。吡唑烷酮被证明是环加成中有效的非手性模板，提供的 C-加合物通常具有 >30:1 的选择性和 80-99% ee。为了避免涉及路易斯酸与胺碱配位的潜在问题，我们设计了一种新方法，使用 Amberlyst 21 作为碱从羟亚胺酰氯生成不稳定的腈氧化物。
• Exo Selective Enantioselective Nitrone Cycloadditions
  作者：Mukund P. Sibi、Zhihua Ma、Craig P. Jasperse

  DOI：10.1021/ja039087p

  日期：2004.1.28

  We have developed a novel method for accessing exo adducts with high enantioselectivity in nitrone cycloadditions to enoates. Pyrazolidinones proved to be effective achiral templates in the cycloadditions, providing exo adducts typically in >15:1 selectivity and 90-98% ee. The use of Lewis acids that form square planar complexes, such as copper triflate, was important for obtaining high exo selectivity.
• Evaluation of Achiral Templates with Fluxional Brønsted Basic Substituents in Enantioselective Conjugate Additions
  作者：Shinya Adachi、Norihiko Takeda、Mukund P. Sibi

  DOI：10.1021/ol503275w

  日期：2014.12.19

  Enantioselective conjugate addition of malononitrile to pyrazolidinone-derived enoates proceeds in excellent yields and high enantioselectivities. A comparison of fluxional substituents with and without a Bronsted basic site and their impact on selectivity is detailed. Molecular sieves as an additive were found to be essential to achieve high enantioselectivity.