(S)-2-[(phenylamino)methyl]cyclohexanone | 840475-21-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (S)-2-[(phenylamino)methyl]cyclohexanone
• 英文别名: (2S)-2-(anilinomethyl)cyclohexan-1-one
• CAS: 840475-21-0
• 化学式: C₁₃H₁₇NO
• 分子量: 203.284
• InChiKey: OFNHBCJJEJFKDQ-NSHDSACASA-N

物化性质

• 熔点：
  85-87 °C
• 沸点：
  360.0±15.0 °C(Predicted)
• 密度：
  1.082±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-2-[(phenylamino)methyl]cyclohexanone 在 tris-(dibenzylideneacetone)dipalladium(0) 、 dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl 、 lithium tert-butoxide 作用下， 以 1,4-二氧六环 、 乙醚 、 水 为溶剂， 反应 14.0h， 生成 (R)-5-phenyl-5,6,6a,7,8,9-hexahydrophenanthridine
  参考文献：
  名称：

  Tosylhydrazide-Promoted Palladium-Catalyzed Reaction of β-Aminoketones witho-Dihaloarenes: Combining Organocatalysis and Transition-Metal Catalysis

  摘要：

  DOI：

  10.1002/anie.201006996
• 作为产物：
  描述：

  聚合甲醛 、 环己酮 、 苯胺 在 L-脯氨酸 作用下， 以 水 、 二甲基亚砜 为溶剂， 以92%的产率得到(S)-2-[(phenylamino)methyl]cyclohexanone
  参考文献：
  名称：

  酮的直接有机催化对映选择性α-氨基甲基化

  摘要：

  公开了酮的直接有机催化不对称α-氨基甲基化的范围和限制。未经修饰的酮，甲醛水溶液和芳族胺之间脯氨酸催化的经典曼尼希反应以高收率提供了所需的曼尼希碱，ee高达99％以上。此外，甲基烷基酮在亚甲基碳上被区域选择性地α-氨基甲基化，从而提供了具有高达> 99％ee的相应曼尼希产品。此外，脯氨酸催化的对苯甲醚，甲醛水溶液和4,4-二甲基-2-环二烯-1-酮之间的一锅三组分反应为相应的双环氮杂-Diels-Alder加合物提供了> 99％ee 。

  DOI：

  10.1016/j.tet.2005.08.113

文献信息

• Thermal Effects in the Organocatalytic Asymmetric Mannich Reaction
  作者：Belén Rodríguez、Carsten Bolm

  DOI：10.1021/jo060064d

  日期：2006.3.31

  The proline-catalyzed direct asymmetric Mannich reaction between cyclohexanone, formaldehyde, and various anilines is thermally accelerated. With only 0.5 mol % of catalyst, Mannich products with up to 98% ee have been obtained after a short period of time in reactions performed under microwave irradiation. In situ reduction of the resulting ketones affords N-aryl amino alcohols in up to 86% yield

  热促进环己酮，甲醛和各种苯胺之间脯氨酸催化的直接不对称曼尼希反应。仅用0.5mol％的催化剂，在微波辐射下进行的短时间反应后，获得了具有高达98％ee的曼尼希产物。原位还原得到的酮可提供高达86％收率的N-芳基氨基醇。
• Inductive Heating with Magnetic Materials inside Flow Reactors
  作者：Sascha Ceylan、Ludovic Coutable、Jens Wegner、Andreas Kirschning

  DOI：10.1002/chem.201002291

  日期：2011.2.7

  can be performed under flow conditions by using inductively heated flow reactors. These include transfer hydrogenations, heterocyclic condensations, pericyclic reactions, organometallic reactions, multicomponent reactions, reductive cyclizations, homogeneous and heterogeneous transition‐metal catalysis. Silica‐coated iron oxide nanoparticles are stable under many chemical conditions and the silica shell

  涂有硅胶或钢珠的超顺磁性纳米粒子是用于流动反应器的新型固定床材料，可在流动条件下有效地加热感应场中的反应混合物。与常规加热和微波加热相比，研究了这些新型加热材料的范围和局限性。结果表明，就速率加速而言，感应加热可以与微波加热进行比较。还证明了通过使用感应加热的流动反应器，可以在流动条件下进行非常多种多样的不同反应。这些包括转移氢化，杂环缩合，周环反应，有机金属反应，多组分反应，还原环化，均相和非均相过渡金属催化。
• Microwave-Assisted Asymmetric Organocatalysis. A Probe for Nonthermal Microwave Effects and the Concept of Simultaneous Cooling
  作者：Masood Hosseini、Nikola Stiasni、Vera Barbieri、C. Oliver Kappe

  DOI：10.1021/jo0624187

  日期：2007.2.1

  [GRAPHICS]A series of five known asymmetric organocatalytic reactions was re-evaluated at elevated temperatures applying both microwave dielectric heating and conventional thermal heating in order to probe the existence of specific or nonthermal microwave effects. All transformations were conducted in a dedicated reactor setup that allowed accurate internal reaction temperature measurements using fiber-optic probes. In addition, the concept of simultaneous external cooling while irradiating with microwave power was also applied in all of the studied cases. This method allows a higher level of microwave power to be administered to the reaction mixture and, therefore, enhances any potential microwave effects while continuously removing heat. For all of the five studied (S)-proline-catalyzed asymmetric Mannich- and aldol-type reactions, the observed rate enhancements were a consequence of the increased temperatures attained by microwave dielectric heating and were not related to the presence of the microwave field. In all cases, in contrast to previous literature reports, the results obtained either with microwave irradiation or with microwave irradiation with simultaneous cooling could be reproduced by conventional heating at the same reaction temperature and time in an oil bath. No evidence for specific or nonthermal microwave effects was obtained.
• Direct Catalytic Enantioselective α-Aminomethylation of Ketones
  作者：Ismail Ibrahem、Jesús Casas、Armando Córdova

  DOI：10.1002/anie.200460678

  日期：2004.12.3
• Direct organocatalytic enantioselective α-aminomethylation of ketones
  作者：Ismail Ibrahem、Weibiao Zou、Jesús Casas、Henrik Sundén、Armando Córdova

  DOI：10.1016/j.tet.2005.08.113

  日期：2006.1

  The scope and limitations of the direct organocatalytic asymmetric α-aminomethylation of ketones are disclosed. The proline-catalyzed classical Mannich reactions between unmodified ketones, aqueous formaldehyde and aromatic amines furnished the desired Mannich bases in high yield with up to >99% ee. Moreover, methyl alkyl ketones were regioselectively α-aminomethylated at the methylene carbon affording

  公开了酮的直接有机催化不对称α-氨基甲基化的范围和限制。未经修饰的酮，甲醛水溶液和芳族胺之间脯氨酸催化的经典曼尼希反应以高收率提供了所需的曼尼希碱，ee高达99％以上。此外，甲基烷基酮在亚甲基碳上被区域选择性地α-氨基甲基化，从而提供了具有高达> 99％ee的相应曼尼希产品。此外，脯氨酸催化的对苯甲醚，甲醛水溶液和4,4-二甲基-2-环二烯-1-酮之间的一锅三组分反应为相应的双环氮杂-Diels-Alder加合物提供了> 99％ee 。