4-oxo-2,6-diphenyl-1,1-cyclohexanedicarbonitrile | 62940-83-4

• 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: 4-oxo-2,6-diphenyl-1,1-cyclohexanedicarbonitrile
• 英文别名: 4-oxo-2,6-diphenylcyclohexane-1,1-dicarbonitrile；(2R,6R)-4-oxo-2,6-diphenylcyclohexane-1,1-dicarbonitrile
• CAS: 62940-83-4
• 化学式: C₂₀H₁₆N₂O
• 分子量: 300.36
• InChiKey: KRKPISNTMFUWNG-RTBURBONSA-N

物化性质

• 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

• 作为反应物：
  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
• 作为产物：
  描述：

  联甲基苯乙烯酮 、 丙二腈 在 2-哌啶甲醇 作用下， 以 甲苯 为溶剂， 生成 4-oxo-2,6-diphenyl-1,1-cyclohexanedicarbonitrile
  参考文献：
  名称：

  奎宁催化双迈克尔加成丙二腈到 1,5-二取代戊二烯-3-酮：环己酮的立体选择性途径

  摘要：

  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。

  DOI：

  10.1002/ejoc.201100282

文献信息

• Bio-Catalytic Bis-Michael Reaction for Generating Cyclohexanones with a Quaternary Carbon Center Using Glucoamylase
  作者：Yong Zhang、Rui Li、Yan-Hong He、Zhi Guan

  DOI：10.1007/s10562-016-1964-6

  日期：2017.3

  the construction of quaternary carbon centers is reported. Glucoamylase from Aspergillus niger (AnGA) was used as a sustainable and eco-friendly catalyst. Various highly substituted trans-cyclohexanones with a quaternary carbon center were obtained with yields of up to 92%. As a novel case of enzyme promiscuity, this work provides a bio-catalytic alternative for construction of quaternary carbon centers

  摘要 报道了用于构建季碳中心的生物催化双迈克尔反应。来自黑曲霉 (AnGA) 的葡糖淀粉酶被用作可持续和环保的催化剂。以高达 92% 的产率获得了各种具有季碳中心的高度取代的反式环己酮。作为酶混杂的一个新案例，这项工作为构建四元碳中心提供了一种生物催化替代方案。图文摘要来自黑曲霉 (AnGA) 的葡糖淀粉酶催化 (1E,4E)-1,5-diarylpenta-的双迈克尔加成1,4-dien-3-ones 与活性亚甲基化合物形成各种具有季碳中心的高度取代的反式环己酮
• Organocatalytic Conjugate Addition of Malononitrile to Conformationally Restricted Dienones
  作者：Zhi-Peng Hu、Chun-Liang Lou、Jin-Jia Wang、Chun-Xia Chen、Ming Yan

  DOI：10.1021/jo200112r

  日期：2011.5.20

  Organocatalytic conjugate addition of malononitrile to conformationally restricted dienones has been studied. A series of chiral primary and tertiary amine catalysts were screened. A piperidine-based thiourea-tertiary amine was found to be the efficient catalyst. Chiral pyran derivatives were obtained in excellent yields and enantioselectivities via a cascade conjugate addition–intramolecular cyclization pathway

  已经研究了丙二腈向构象受限的二烯酮的有机催化共轭加成。筛选了一系列手性伯胺和叔胺催化剂。发现基于哌啶的硫脲叔胺是有效的催化剂。通过级联共轭加成-分子内环化途径获得了高收率和对映选择性的手性吡喃衍生物。对于构象柔性二烯酮的相应反应，该反应明显不同。
• 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.
• Structures of Marvel's .delta.-lactone and polymer
  作者：Alex T. Rowland、Benjamin C. Gill

  DOI：10.1021/jo00237a042

  日期：1988.1
• ROWLAND, ALEX T.;GILL, BENJAMIN C., J. ORG. CHEM., 53,(1988) N 2, 434-437
  作者：ROWLAND, ALEX T.、GILL, BENJAMIN C.

  DOI：——

  日期：——