syn-2-[(p-nitrophenyl)(phenylamino)methyl]cyclohexanone

• 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: syn-2-[(p-nitrophenyl)(phenylamino)methyl]cyclohexanone
• 英文别名: 2-((4-nitrophenyl)(phenylamino)methyl)cyclohexan-1-one；2-[(p-nitrophenyl)(phenylamino)methyl]cyclohexanone；2-[(4-nitrophenyl)(phenylamino)methyl]cyclohexanone；2-[(phenylamino)(4-nitrophenyl)methyl]cyclohexanone；rac-(R)-2-((R)-(4-nitrophenyl)(phenylamino)methyl)cyclohexanone；(2S)-2-[(S)-anilino-(4-nitrophenyl)methyl]cyclohexan-1-one
• 化学式: C₁₉H₂₀N₂O₃
• 分子量: 324.379
• InChiKey: NYIIUYQEHABPRN-IEBWSBKVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  74.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (4-nitro-benzylidene)-phenyl-amine 、 1-trichloroacetoxycyclohexene 在 二丁基二甲氧基锡 甲醇 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 syn-2-[(p-nitrophenyl)(phenylamino)methyl]cyclohexanone 、 (R)-2-((S)-(4-nitrophenyl)(phenylamino)methyl)cyclohexanone
  参考文献：
  名称：

  二甲基二丁基锡催化三烯基乙酸乙酸酯的曼尼希型反应

  摘要：

  通过使用二甲醇二丁基锡作为催化剂，可以实现三氯乙酸烯基酯与醛亚胺的新型曼尼希型反应，该反应可通过添加甲醇进行再生。醛，伯胺和烯基三氯乙酸酯的三组分偶联反应也已经有效地实现。这些程序可提供多种β氨基不仅从芳族醛也有来自α，β不饱和醛主要与酮的合成在高产率高达99％ -选择性。

  DOI：

  10.1002/adsc.200505156

文献信息

• Enantioselective Mannich Reactions with the Practical Proline Mimetic <i>N</i>-(<i>p</i>-Dodecylphenyl-sulfonyl)-2-pyrrolidinecarboxamide
  作者：Hua Yang、Rich G. Carter

  DOI：10.1021/jo8027938

  日期：2009.3.6

  highly enantioselective and diastereoselective protocol for performing Mannich reactions has been developed by using a p-dodecylphenylsulfonamide-based proline catalyst. This catalyst facilitates the use of common, nonpolar solvents and increased concentrations as compared to alternative methods. A series of syn-selective Mannich reactions is reported, including the rapid access of α- and β-amino acids surrogates

  通过使用基于对十二烷基苯基磺酰胺的脯氨酸催化剂，已经开发出用于进行曼尼希反应的高度对映选择性和非对映选择性的方案。与替代方法相比，该催化剂促进了普通非极性溶剂的使用并提高了浓度。一系列的顺式-选择性曼尼希反应报道，包括α-和β氨基酸替代物的快速存取。还证明了使用工业上有吸引力的非极性溶剂，例如2-甲基-四氢呋喃。
• 5-Sulfosalicylic acid catalyzed direct Mannich reaction in pure water
  作者：Chun Chen、Xuyang Zhu、Ya Wu、Huaming Sun、Guofang Zhang、Weiqiang Zhang、Ziwei Gao

  DOI：10.1016/j.molcata.2014.08.017

  日期：2014.12

  A water-soluble Brønsted acid, 5-sulfosalicylic acid, efficiently catalyzed the direct three-component Mannich reactions of cyclohexanone and 3-pentanone in pure water. 21 Examples of Mannich reactions were presented, which afforded the corresponding β-amino ketones with up to 97% yield and decent diastereoselectivities. The acid catalyst can be recycled as an aqueous solution for at least six times

  水溶性布朗斯台德酸5-磺基水杨酸可在纯水中有效催化环己酮和3-戊酮的直接三组分曼尼希反应。给出了21个Mannich反应的例子，该例子提供了相应的β-氨基酮，产率高达97％，非对映选择性也不错。酸催化剂可以水溶液形式循环至少六次，曼尼希产品的产率保持在90％以上。
• Solvent strategy for unleashing the Lewis acidity of titanocene dichloride for rapid Mannich reactions
  作者：Ya Wu、Xiu Wang、Yanlong Luo、Jing Wang、Yajun Jian、Huaming Sun、Guofang Zhang、Weiqiang Zhang、Ziwei Gao

  DOI：10.1039/c5ra27094d

  日期：——

  The remarkable activation effect of alcohol solvent on kinetically inert titanocene dichloride was found to promote rapid three-component Mannich reactions. NMR and ESI-MS analyses as well as a control experiment of catalytic active species elucidated that the coordination of MeOH to the titanocene moiety unleashed the Lewis acid [Cp2Ti(OMe)2] and Brønsted acid HCl, which led to the enhanced catalytic

  发现醇溶剂对动力学惰性二茂钛二氯化物的显着活化作用促进了快速的三组分曼尼希反应。NMR和ESI-MS分析以及催化活性物种的对照实验表明，MeOH与二茂钛部分的配位释放出路易斯酸[Cp 2 Ti（OMe）2 ]和布朗斯台德HCl，从而增强了催化作用Cp 2 TiCl 2的活性。
• Direct Asymmetric Mannich Reaction Catalyzed by a d-Glucosamine-Derived Organocatalyst
  作者：Rama Peddinti、Arun Sharma

  DOI：10.1055/s-0036-1591740

  日期：2018.3

  Sugar-based primary amines have been employed as organocatalysts for the direct asymmetric Mannich reaction. By catalyst-screening experiments, we observed that catalysts bearing a hydroxy function at C-3 actively participated in the reaction, possibly through hydrogen bonding with the imine generated in situ, to provide β-amino carbonyl compounds with better diastereoselectivity and enantioselectivity

  糖基伯胺已被用作直接不对称曼尼希反应的有机催化剂。通过催化剂筛选实验，我们观察到在 C-3 处带有羟基官能团的催化剂积极参与反应，可能是通过与原位生成的亚胺形成氢键，从而提供具有更好非对映选择性和对映选择性的 β-氨基羰基化合物。获得的所有产品都处于良好至极好的对映体过量。
• 2-Pyrrolidinecarboxylic Acid Ionic Liquid as a Highly Efficient Organocatalyst for the Asymmetric One-Pot Mannich Reaction
  作者：Xin Zheng、Yun-Bo Qian、Yongmei Wang

  DOI：10.1002/ejoc.200901088

  日期：2010.1

  A novel one-pot three-component asymmetric Mannich reaction using [EMIm][Pro] (1) as a catalyst has been developed. By employing this new reaction system, a variety of optically active β-amino carbonyl compounds were synthesized in up to 99 % yield with up to >99 dr and >99 % ee. The reaction conditions have been optimized and the mechanism for the asymmetric induction is discussed.

  已经开发了一种使用 [EMIm][Pro] (1) 作为催化剂的新型一锅三组分不对称曼尼希反应。通过采用这种新的反应系统，合成了多种光学活性 β-氨基羰基化合物，产率高达 99%，高达 >99 dr 和 >99% ee。优化了反应条件并讨论了不对称诱导的机制。