(S,R)-4-oxo-2,6-diphenyl-1,1-cyclohexanedicarbonitrile | 143287-16-5

• 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: (S,R)-4-oxo-2,6-diphenyl-1,1-cyclohexanedicarbonitrile
• 英文别名: (2R,6S)-4-oxo-2,6-diphenylcyclohexane-1,1-dicarbonitrile
• CAS: 143287-16-5
• 化学式: C₂₀H₁₆N₂O
• 分子量: 300.36
• InChiKey: KRKPISNTMFUWNG-KDURUIRLSA-N

物化性质

• 熔点：
  211.5-212.5 °C
• 沸点：
  552.7±50.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4-oxo-2,6-diphenyl-1,1-cyclohexanedicarbonitrile 在 苄基三甲基氢氧化铵 作用下， 以 乙醇 为溶剂， 反应 1.1h， 以85%的产率得到(S,R)-4-oxo-2,6-diphenyl-1,1-cyclohexanedicarbonitrile
  参考文献：
  名称：

  On the Stereochemistry of Diaryl-Substituted Cyclohexanones Formed by Michael Reactions. Trans to Cis Isomerization of Their Ketals under Basic Conditions

  摘要：

  The stereochemistry of C-1-substituted 2,6-diphenylcyclohexan-4-ones 1-3 prepared by Michael reactions has been investigated. While preparations of these compounds have been reported over the past 70 years, in many instances the correct stereochemistry at C-2 (6) and, in some instances at C-1, was uncertain. We show here that in one case in which two identical substituents (CN) are present at C-1, it is possible to isomerize the initially formed trans isomer Id to the cis isomer 3f. When a cyano group and a dissimilar substituent are present at C-1, the initially formed trans isomer may be isomerized to the cis compound. The stereochemistry is vertified by NMR spectroscopy and by X-ray analysis. Reaction of the ethylene ketals (4 and 5) of these ketones with KOH in DMSO at elevated temperatures gives rise to cis products, and deuterium-labeling studies demonstrated the acidity of the benzylic hydrogen at C-2 (6). Isomerization was evident since the trans ketal 4a and the cis ketal 4b gave the same amide 6a. H-1 and C-13 NMR spectra provided conclusive evidence for the cis - trans rearrangement.

  DOI：

  10.1021/jo9801059

文献信息

• Quinine-Catalysed Double Michael Addition of Malononitrile to 1,5-Disubstituted Pentadien-3-ones: A Stereoselective Route to Cyclohexanones
  作者：Claudia De Fusco、Alessandra Lattanzi

  DOI：10.1002/ejoc.201100282

  日期：2011.7

  The stereoselective synthesis of 4-oxo-2,6-diaryl-cyclohexane-1,1-dicarbonitriles has been developed through double Michael addition of malononitrile to 1,5-disubstituted pentadien-3-ones catalysed by quinine. This simple cascade process affords cyclohexanones in moderate-to-good yields, excellent diastereoselectivity and up to 86 % ee. The isolation of the monoaddition product helps to shed light

  4-氧代-2,6-二芳基-环己烷-1,1-二腈的立体选择性合成是通过丙二腈与奎宁催化的1,5-二取代戊二烯-3-酮的双迈克尔加成而开发的。这种简单的级联过程以中等至良好的产率、出色的非对映选择性和高达 86% 的 ee 提供了环己酮。单加成产物的分离有助于阐明两步法的立体化学结果。
• Asymmetric Organocatalytic Double-Conjugate Addition of Malononitrile to Dienones: Efficient Synthesis of Optically Active Cyclohexanones
  作者：Xue-ming Li、Bo Wang、Jun-min Zhang、Ming Yan

  DOI：10.1021/ol102570b

  日期：2011.2.4

  9-Amino-9-deoxyepiquinine efficiently catalyzed the double-conjugate addition of malononitrile to dienones. A number of 1,1,2,6-tetrasubstituted cyclohexanones were prepared in good yields, diastereoselectivities, and excellent enantioselectivities.