1-(3,5-bis(trifluoromethyl)phenyl)-3-((1R,2R)-2-((4-(dimethylamino)pyridin-2-yl)amino)cyclohexyl)thiourea | 1421748-76-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-(3,5-bis(trifluoromethyl)phenyl)-3-((1R,2R)-2-((4-(dimethylamino)pyridin-2-yl)amino)cyclohexyl)thiourea
• 英文别名: 2-N-[(1R,2R)-2-aminocyclohexyl]-4-N,4-N-dimethylpyridine-2,4-diamine
• CAS: 1421748-76-6
• 化学式: C₁₃H₂₂N₄
• 分子量: 234.344
• InChiKey: GNYOSLAJIGOXPP-VXGBXAGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  54.2
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(3,5-bis(trifluoromethyl)phenyl)-3-((1R,2R)-2-((4-(dimethylamino)pyridin-2-yl)amino)cyclohexyl)thiourea 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 25.0h， 生成 N-[(1R,2R)-2-[[4-(dimethylamino)pyridin-2-yl]amino]cyclohexyl]-1-[(1S,2R,4R)-2-hydroxy-7,7-dimethyl-1-bicyclo[2.2.1]heptanyl]methanesulfonamide
  参考文献：
  名称：

  Cu-Catalyzed Selective Mono-N-pyridylation: Direct Access to 2-AminoDMAP/Sulfonamides as Bifunctional Organocatalysts

  摘要：

  Direct and selective mono-N-pyridylation of trans-(R,R)-cyclohexane-1,2-diamine is described here. Facile preparation of a novel chiral 2-aminoDMAP core catalaphore via Cu catalysis has led to the development of various sulfonamide/2-aminoDMAPs as bifunctional acid/base organocatalysts (most in two steps overall), which have been shown to very effectively promote asymmetric conjugate addition of acetylacetone to trans-beta-nitroolefins with good to excellent yields (87-93%) and enantioselectivites (up to 99%).

  DOI：

  10.1021/jo302713b
• 作为产物：
  描述：

  2-((1R,2R)-2-aminocyclohexyl)isoindoline-1,3-dione 在 palladium diacetate 、 caesium carbonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 一水合肼 作用下， 以 乙醇 、 氘代甲苯 为溶剂， 反应 62.0h， 生成 1-(3,5-bis(trifluoromethyl)phenyl)-3-((1R,2R)-2-((4-(dimethylamino)pyridin-2-yl)amino)cyclohexyl)thiourea
  参考文献：
  名称：

  Cu-Catalyzed Selective Mono-N-pyridylation: Direct Access to 2-AminoDMAP/Sulfonamides as Bifunctional Organocatalysts

  摘要：

  Direct and selective mono-N-pyridylation of trans-(R,R)-cyclohexane-1,2-diamine is described here. Facile preparation of a novel chiral 2-aminoDMAP core catalaphore via Cu catalysis has led to the development of various sulfonamide/2-aminoDMAPs as bifunctional acid/base organocatalysts (most in two steps overall), which have been shown to very effectively promote asymmetric conjugate addition of acetylacetone to trans-beta-nitroolefins with good to excellent yields (87-93%) and enantioselectivites (up to 99%).

  DOI：

  10.1021/jo302713b

文献信息

• Modularly Evolved 2-AminoDMAP/Squaramides as Highly Active Bifunctional Organocatalysts in Michael Addition
  作者：Murat Işık、M. Yagiz Unver、Cihangir Tanyeli

  DOI：10.1021/jo5022597

  日期：2015.1.16

  We report a new family of chiral bifunctional acid/base type organocatalysts, 2-aminoDMAP/Squaramides, which are proved to be highly active (1 mol % cat. loading) promoters in conjugate addition of dibenzoylmethane to various trans-β-nitroalkenes. Steric demand of the catalysts was clearly seen by a set-by-set modulation of the squaramide unit through electronic and steric factors. The synergistic

  我们报道了一个新的手性双官能酸/碱型有机催化剂，2-aminoDMAP / Squaramides家族，被证明是在将二苯甲酰甲烷共轭加成到各种反式-β-硝基烯烃中的高活性（1 mol％催化剂负载量）促进剂。通过电子和空间因素对方酰胺单元进行逐组调节，可以清楚地看到催化剂的立体需求。2-氨基DMAP“超强碱”与空间受限的方酰胺（氢键供体）的协同作用，使得在短短几个小时内即可将一系列反应物完全转化为相应的迈克尔加成物，且选择性极高（ee高达98％）。
• A Dual-Catalysis Anion-Binding Approach to the Kinetic Resolution of Amines: Insights into the Mechanism via a Combined Experimental and Computational Study
  作者：Nisha Mittal、Katharina M. Lippert、Chandra Kanta De、Eric G. Klauber、Thomas J. Emge、Peter R. Schreiner、Daniel Seidel

  DOI：10.1021/jacs.5b00190

  日期：2015.5.6

  Racemic benzylic amines undergo kinetic resolution via benzoylation with benzoic anhydride in the presence of a dual catalyst system consisting of a readily available amide-thiourea catalyst and 4-dimethylaminopyridine (DMAP). An evaluation of various experimental parameters was performed in order to derive a more detailed understanding of what renders this process selective. The catalyst's aggregation behavior and anion-binding ability were evaluated in regard to their relevance for the catalytic process. Alternate scenarios, such as catalyst deprotonation or the in situ formation of a neutral chiral acylating reagent were ruled out. Detailed computational studies at the M06/6-31G(d,p) level of theory including solvent modeling utilizing a polarized continuum model provide additional insights into the nature of the ion pair and reveal a range of important secondary interactions that are responsible for efficient enantiodiscrimination.
• A bis-Lewis basic 2-aminoDMAP/prolinamide organocatalyst for application to the enantioselective synthesis of Warfarin and derivatives
  作者：Murat Işık、H. Ufuk Akkoca、İ. Mecidoğlu Akhmedov、Cihangir Tanyeli

  DOI：10.1016/j.tetasy.2016.04.001

  日期：2016.6

  A new chiral sec-amine/amidine-base hybrid catalyst, 2-aminoDMAP/prolinamide, is reported, which is able to catalyze conjugate addition of 4-hydroxycoumarin and various benzylideneacetones, a reaction that directly gives anticoagulant Warfarin and its analogues, with good yields (70-87%) and enantioselectivities (58-72%). (C) 2016 Elsevier Ltd. All rights reserved.
• Cu-Catalyzed Selective Mono-<i>N</i>-pyridylation: Direct Access to 2-AminoDMAP/Sulfonamides as Bifunctional Organocatalysts
  作者：Murat Isik、Cihangir Tanyeli

  DOI：10.1021/jo302713b

  日期：2013.2.15

  Direct and selective mono-N-pyridylation of trans-(R,R)-cyclohexane-1,2-diamine is described here. Facile preparation of a novel chiral 2-aminoDMAP core catalaphore via Cu catalysis has led to the development of various sulfonamide/2-aminoDMAPs as bifunctional acid/base organocatalysts (most in two steps overall), which have been shown to very effectively promote asymmetric conjugate addition of acetylacetone to trans-beta-nitroolefins with good to excellent yields (87-93%) and enantioselectivites (up to 99%).