3-isopropenyl-1-(toluene-4-sulfonyl)piperidin-4-one | 694526-59-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-isopropenyl-1-(toluene-4-sulfonyl)piperidin-4-one
• 英文别名: 1-(4-Methylphenyl)sulfonyl-3-prop-1-en-2-ylpiperidin-4-one；1-(4-methylphenyl)sulfonyl-3-prop-1-en-2-ylpiperidin-4-one
• CAS: 694526-59-5
• 化学式: C₁₅H₁₉NO₃S
• 分子量: 293.387
• InChiKey: ZDNYDABFSGUGAY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  62.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-isopropenyl-1-(toluene-4-sulfonyl)piperidin-4-one 在 二异丁基氢化铝 、 异丙醇 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以79%的产率得到(3RS,4RS)-3-isopropenyl-1-(toluene-4-sulfonyl)piperidin-4-ol
  参考文献：
  名称：

  Synthesis of 3-Substituted 4-Piperidinones via a One-Pot Tandem Oxidation−Cyclization−Oxidation Process:  Stereodivergent Reduction to 3,4-Disubstituted Piperidines

  摘要：

  A novel approach to 3-substituted 4-piperidinones is described. The one-pot tandem oxidation - cyclization - oxidation of unsaturated alcohols 1a-e by PCC or PCC and trifluoromethanesulfonic acid affords piperidinones 2a-e in good yield. Reduction of 2a-e by L-Selectride gives the corresponding cis 3,4-disubstituted piperidines with diastereomeric ratios of >99:1. By contrast, reduction of 2a-e by Al-isopropoxydiisobutylalane gives the trans products with diastereomeric ratios of up to 99:1.

  DOI：

  10.1021/jo0357418
• 作为产物：
  描述：

  N-(3-hydroxypropyl)-4-methyl-N-(3-methylbut-2-enyl)benzenesulfonamide 在 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 240.0h， 以64%的产率得到3-isopropenyl-1-(toluene-4-sulfonyl)piperidin-4-one
  参考文献：
  名称：

  Synthesis of 3-Substituted 4-Piperidinones via a One-Pot Tandem Oxidation−Cyclization−Oxidation Process:  Stereodivergent Reduction to 3,4-Disubstituted Piperidines

  摘要：

  A novel approach to 3-substituted 4-piperidinones is described. The one-pot tandem oxidation - cyclization - oxidation of unsaturated alcohols 1a-e by PCC or PCC and trifluoromethanesulfonic acid affords piperidinones 2a-e in good yield. Reduction of 2a-e by L-Selectride gives the corresponding cis 3,4-disubstituted piperidines with diastereomeric ratios of >99:1. By contrast, reduction of 2a-e by Al-isopropoxydiisobutylalane gives the trans products with diastereomeric ratios of up to 99:1.

  DOI：

  10.1021/jo0357418

文献信息

• Gold(I)-catalyzed benzannulation of 3-hydroxy-1,5-enynes: an efficient synthesis of substituted tetrahydronaphthalenes and related compounds
  作者：Christiane M. Grisé、Eric M. Rodrigue、Louis Barriault

  DOI：10.1016/j.tet.2007.10.084

  日期：2008.1

  We report a novel gold(I)-catalyzed benzannulation of 3-hydroxy-1,5-enynes to prepare tetrahydronaphthalenes. The reaction is catalyzed by 2.5 mol % Ph3PAuCl and 2.5 mol % AgOTf in dichloromethane. We discovered that this process can be also catalyzed by 1 mol % Ph3PAuCl and 1 mol % TfOH. To the best of our knowledge, this constitutes the first report of an active gold catalyst generated from Au(PPh3)Cl

  我们报告了一种新型的金（I）催化3-羟基-1,5-烯炔的苯并环烷制备四氢萘。该反应由在二氯甲烷中的2.5mol％的Ph 3 PAuCl和2.5mol％的AgOTf催化。我们发现，该过程也可以由1 mol％的Ph 3 PAuCl和1 mol％的TfOH催化。据我们所知，这是由Au（PPh 3）Cl和三氟甲磺酸生成的活性金催化剂的首次报道。该温和的方法与各种官能团相容，并且被证明是以高收率合成各种间位取代的芳族环的有效方法。
• Kinetic, Thermodynamic, and Dynamic Control in Normal vs. Cross [2 + 2] Cycloadditions of Ene-Keteniminium Ions: Computational Understanding, Prediction, and Experimental Verification
  作者：Pan Zhang、Zhi-Xiang Yu

  DOI：10.1021/jacs.3c00685

  日期：2023.5.3

  Almost all reported intramolecular [2 + 2] reactions of ene-keteniminium ions gave normal [2 + 2] products with a fused bicycle framework, but not cross [2 + 2] products with a bicyclo[3.1.1]heptane skeleton, a highly pursued bioisostere in pharmaceutical chemistry. How to rationalize this and design new cross [2 + 2] reactions? Theoretical studies using density functional theory, high-level ab initio

  几乎所有报道的烯-烯酮亚胺离子的分子内 [2 + 2] 反应都会产生具有稠合自行车骨架的正常 [2 + 2] 产物，但不会产生具有双环 [3.1.1] 庚烷骨架的交叉 [2 + 2] 产物，a药物化学中高度追求的生物电子等排体。如何合理化并设计新的交叉 [2 + 2] 反应？使用密度泛函理论、高水平从头算单点能量计算和分子动力学的理论研究表明，这种 [2 + 2] 反应具有所有三种区域化学控制模式：反应受动力学、热力学或动态控制。形成内切和外切的碳阳离子模型已提出碳正离子以使反应结果合理化，揭示了链（烯烃和烯酮亚胺离子之间）、取代基（在烯烃上）和烯-烯酮亚胺离子中的烯烃构型起着关键作用。这些认识进一步用于预测在具有反式的烯烃的末端位置引入取代基烯-烯酮亚胺离子中的构型可以实现交叉[2+2]反应，该反应对烷基取代基是动态控制的，对芳基取代基是动力学控制的。这些和更多其他预测都通过实验实现了，并且可以实现许多具有双环[3
• Synthesis of 3-Substituted 4-Piperidinones via a One-Pot Tandem Oxidation−Cyclization−Oxidation Process:  Stereodivergent Reduction to 3,4-Disubstituted Piperidines
  作者：Perdip S. Bahia、John S. Snaith

  DOI：10.1021/jo0357418

  日期：2004.4.1

  A novel approach to 3-substituted 4-piperidinones is described. The one-pot tandem oxidation - cyclization - oxidation of unsaturated alcohols 1a-e by PCC or PCC and trifluoromethanesulfonic acid affords piperidinones 2a-e in good yield. Reduction of 2a-e by L-Selectride gives the corresponding cis 3,4-disubstituted piperidines with diastereomeric ratios of >99:1. By contrast, reduction of 2a-e by Al-isopropoxydiisobutylalane gives the trans products with diastereomeric ratios of up to 99:1.