(1R,2R)-N-benzyl-N-methylcyclohexane-1,2-diamine | 834917-67-8

• 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: (1R,2R)-N-benzyl-N-methylcyclohexane-1,2-diamine
• 英文别名: (1R,2R)-N¹-benzyl-N¹-methylcyclohexane-1,2-diamine；(1R,2R)-2-N-benzyl-2-N-methylcyclohexane-1,2-diamine
• CAS: 834917-67-8
• 化学式: C₁₄H₂₂N₂
• 分子量: 218.342
• InChiKey: FTAQCJUQTAEZTC-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  29.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-氯甲酰吡啶 、 (1R,2R)-N-benzyl-N-methylcyclohexane-1,2-diamine 以 二氯甲烷 为溶剂， 反应 4.0h， 以86%的产率得到2-N,6-N-bis[(1R,2R)-2-[benzyl(methyl)amino]cyclohexyl]pyridine-2,6-dicarboxamide
  参考文献：
  名称：

  Cycloalkane-1,2-diamine derivatives as chiral solvating agents. Study of the structural variables controlling the NMR enantiodiscrimination of chiral carboxylic acids

  摘要：

  A family of pincer-like receptors (2-5) has been synthesized and tested for the NMR enantiodiscrimination (CSA) of chiral carboxylic acids. Starting from a previous design (1), different structural variables have been mapped on the receptor frame. The splitting of the signals of the acids upon the addition of the CSAs largely depends on these structural variables. Thus, we concluded that the C-2 symmetrical pyridine-2,6-biscarboxamide moiety is a key structural feature for the efficiency of the CSA. Structural studies by NMR and molecular modeling showed that this moiety promotes the U-shape-folded pincer-like conformation by intramolecular H-bonds. On the other hand, we also observed that the cyclohexane-1,2-diamine derivative 5 is a more versatile CSA than its cyclopentane analogue 1, as 5 shows a better performance for more structurally different acids. However, the original cyclopentane derivative (1) remained the best for the arylpropionic acids. Finally, combination of NMR and modeling studies allowed us to propose a reasonable model for the interaction and, accordingly, for the observed NMR enantiodiscrimination. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.06.031
• 作为产物：
  描述：

  在 盐酸 、 sodium hydroxide 作用下， 以 水 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 (1R,2R)-N-benzyl-N-methylcyclohexane-1,2-diamine
  参考文献：
  名称：

  A chiral primary-tertiary-1,2-diamine as an efficient catalyst in asymmetric aldehyde–ketone or ketone–ketone aldol reactions

  摘要：

  A novel chiral 1,2-diaminocyclohexane derivative, (1R,2R)-N-1-n-pentyl, N-1-benzyl-1,2-cyclohexanediamine, was designed, synthesized and applied as a catalyst in a number of aldol reactions between ketones and aryl aldehydes. Reactions between acetone and aryl aldehydes gave aldol products with moderate to good yields and with excellent enantioselectivity (up to yield 85%, ee 98%), while reactions between cyclohexanone and aryl aldehydes provided anti-beta-hydroxyketone products with excellent yields, diastereoselectivity and with enantioselectivity (up to 82% yield, anti/syn ratio 99:1, ee 99%). The aldol reactions between acetone and isatins were investigated, which afforded excellent yields and enantioselectivity (up to 95% yield, 98% ee). The (R)- and (S)-isomers of convolutamydine A were obtained with 95% yield and 96% ee, and 95% yield and 94% ee, respectively. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.09.026

文献信息

• Structural optimization of thiourea-based bifunctional organocatalysts for the highly enantioselective dynamic kinetic resolution of azlactones
  作者：Albrecht Berkessel、Santanu Mukherjee、Thomas N. Müller、Felix Cleemann、Katrin Roland、Marc Brandenburg、Jörg-M. Neudörfl、Johann Lex

  DOI：10.1039/b607574f

  日期：——

  describes the synthesis of a library of structurally diverse bifunctional organocatalysts bearing both a quasi-Lewis acidic (thio)urea moiety and a Bronsted basic tertiary amine group. Sequential modification of the modular catalyst structure and subsequent screening of the compounds in the alcoholytic dynamic kinetic resolution (DKR) of azlactones revealed valuable structure-activity relationships. In particular

  本文介绍了结构多样的双功能有机催化剂库的合成，该催化剂同时具有准路易斯酸（硫）脲部分和布朗斯台德碱性叔胺基团。模块化催化剂结构的顺序修饰和随后的内酯​​内醇动力学动力学拆分（DKR）中的化合物的筛选揭示了宝贵的结构-活性关系。特别地，鉴定出“命中结构”，其以优异的对映体过量95％提供例如N-苯甲酰基-叔亮氨酸烯丙基酯。
• Enantio- and Diastereoselective Michael Reaction of 1,3-Dicarbonyl Compounds to Nitroolefins Catalyzed by a Bifunctional Thiourea
  作者：Tomotaka Okino、Yasutaka Hoashi、Tomihiro Furukawa、Xuenong Xu、Yoshiji Takemoto

  DOI：10.1021/ja044370p

  日期：2005.1.1

  thiourea moiety and an amino group on a chiral scaffold. Among them, thiourea 1e bearing 3,5-bis(trifluoromethyl)benzene and dimethylamino groups was revealed to be highly efficient for the asymmetric Michael reaction of 1,3-dicarbonyl compounds to nitroolefins. Furthermore, we have developed a new synthetic route for (R)-(-)-baclofen and a chiral quaternary carbon center with high enantioselectivity by Michael

  我们在手性支架上合成了一类带有硫脲部分和氨基的新型双功能催化剂。其中，带有 3,5-双（三氟甲基）苯和二甲氨基的硫脲 1e 被证明对于 1,3-二羰基化合物到硝基烯烃的不对称迈克尔反应非常有效。此外，我们通过迈克尔反应开发了 (R)-(-)-巴氯芬和具有高对映选择性的手性季碳中心的新合成路线。在这些反应中，我们假设催化剂的硫脲部分和氨基分别活化硝基烯烃和 1,3-二羰基化合物，以提供具有高对映选择性和非对映选择性的迈克尔加合物。
• Chemoenzymatic Preparation of Optically Active<i>trans</i>-Cyclohexane-1,2-diamine Derivatives: An Efficient Synthesis of the Analgesic U-(−)-50,488
  作者：Javier González-Sabín、Vicente Gotor、Francisca Rebolledo

  DOI：10.1002/chem.200400607

  日期：2004.11.19

  Stereoespecific syntheses of (+/-)-trans-N,N-cyclohexane-1,2-diamines ((+/-)-4 a-g) were carried out from the corresponding (+/-)-trans-N,N-dialkylaminocyclohexanols by successive treatment with mesyl chloride and aqueous ammonia. The stereochemical outcome indicates the formation of a meso-aziridinium ion intermediate. Kinetic resolutions of diamines (+/-)-4 were efficiently accomplished in aminolysis

  （+/-）-反-N，N-环己烷-1,2-二胺（（+/-）-4 ag）的立体定向合成是从相应的（+/-）-反-N，N-通过连续用甲磺酰氯和氨水处理二烷基氨基环己醇。立体化学结果表明形成了中叠氮鎓离子中间体。二胺（+/-）-4的动力学拆分可有效地完成南极假丝酵母脂肪酶B催化的氨解反应，其中乙酸乙酯为溶剂和酰基供体。分离出的乙酰胺和其余的二胺作为苄氧羰基衍生物，具有很高的ee值（92-99％）。一种氨基甲酸酯用作镇痛剂U-（-）-50,488的前体。
• Rapid stereoselective reduction of thermally labile 2-aminonitroalkanes.
  作者：Michael A. Sturgess、David J. Yarberry

  DOI：10.1016/s0040-4039(00)74077-9

  日期：1993.7

  Samarium diiodide may be employed in the stereoselective reduction of thermally unstable 2-aminonitroalkanes to give a range of useful 1,2-diamines.
• Cycloalkane-1,2-diamine derivatives as chiral solvating agents. Study of the structural variables controlling the NMR enantiodiscrimination of chiral carboxylic acids
  作者：Carmen Peña、Javier González-Sabín、Ignacio Alfonso、Francisca Rebolledo、Vicente Gotor

  DOI：10.1016/j.tet.2008.06.031

  日期：2008.8

  A family of pincer-like receptors (2-5) has been synthesized and tested for the NMR enantiodiscrimination (CSA) of chiral carboxylic acids. Starting from a previous design (1), different structural variables have been mapped on the receptor frame. The splitting of the signals of the acids upon the addition of the CSAs largely depends on these structural variables. Thus, we concluded that the C-2 symmetrical pyridine-2,6-biscarboxamide moiety is a key structural feature for the efficiency of the CSA. Structural studies by NMR and molecular modeling showed that this moiety promotes the U-shape-folded pincer-like conformation by intramolecular H-bonds. On the other hand, we also observed that the cyclohexane-1,2-diamine derivative 5 is a more versatile CSA than its cyclopentane analogue 1, as 5 shows a better performance for more structurally different acids. However, the original cyclopentane derivative (1) remained the best for the arylpropionic acids. Finally, combination of NMR and modeling studies allowed us to propose a reasonable model for the interaction and, accordingly, for the observed NMR enantiodiscrimination. (C) 2008 Elsevier Ltd. All rights reserved.