乙基2-(苯基甲基氨基)环己烯-1-羧酸酯 | 38778-78-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 乙基2-(苯基甲基氨基)环己烯-1-羧酸酯
• 英文名称: ethyl 2-(benzylamino)cyclohex-1-ene-1-carboxylate
• 英文别名: (Z)-ethyl-3-(benzylamino)cyclohex-2-enoate；ethyl 3-(benzylamino)cyclohexene-2-enoate；2-benzylamino-cyclohex-1-enecarboxylic acid ethyl ester；ethyl 2-[(benzyl)amino]cyclohexene-1-carboxylate；2-Benzylamino-1-cyclohexencarbonsaeure-ethylester；1-Benzylamino-2-ethoxycarbonyl-cyclohexen；Ethyl 2-((benzyl)amino)cyclohexene-1-carboxylate；ethyl 2-(benzylamino)cyclohexene-1-carboxylate
• CAS: 38778-78-8
• 化学式: C₁₆H₂₁NO₂
• 分子量: 259.348
• InChiKey: SZJAFTIFKQOVPU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

• 海关编码：
  2922499990

反应信息

• 作为反应物：
  描述：

  乙基2-(苯基甲基氨基)环己烯-1-羧酸酯 在 盐酸羟胺 、 sodium methylate 作用下， 反应 4.0h， 生成 4,5,6,7-tetrahydro-1H-benzo[c]isoxazol-3-one
  参考文献：
  名称：

  Organic Hydroxylamine Derivatives. VII. Isoxazolin-5-ones. An Investigation of a Reaction Sequence Previously Stated to Give 3-Hydroxyisoxazoles.

  摘要：

  DOI：

  10.3891/acta.chem.scand.27-2802
• 作为产物：
  描述：

  2-环己酮甲酸乙酯 、 苄胺 在 iron(III) trifluoromethanesulfonate 作用下， 以 neat (no solvent) 为溶剂， 以70%的产率得到乙基2-(苯基甲基氨基)环己烯-1-羧酸酯
  参考文献：
  名称：

  烯胺的氧化还原性质。

  摘要：

  烯胺是具有有趣的氧化还原特性的富电子化合物。在此，合成了由伯胺和β-酮羰基缩合而成的一系列仲烯胺，并通过循环伏安法系统地研究了它们的电化学氧化性能。此外，还进行了烯胺特别是那些催化中间体的氧化电位的理论计算，以进一步拓宽研究范围。揭示和讨论了可能的结构因素对氧化和所得自由基阳离子中间体的性质。探索了氧化还原电势与分子特性（例如最大占据分子轨道能量和自然种群分析电荷）的相关性，并且似乎没有简单的线性相关性。另一方面，与Mayr'的相关性很好 在一系列催化相关的烯胺中注意到其亲核参数N。自旋种群分析表明，烯胺自由基阳离子主要表现出碳中心自由基的特征。综合实验数据和计算数据，可以得出有关烯胺的氧化还原特性的全面图片，这将为氧化烯胺催化和转化的发展提供指导。

  DOI：

  10.1021/acs.joc.9b02003

文献信息

• Vanadium(IV) acetylacetonate catalyzed stereoselective synthesis of β-enaminoesters and β-enaminones
  作者：Rajibul A. Laskar、Naznin A. Begum、Mohammad Hedayetullah Mir、Shahzad Ali、Abu T. Khan

  DOI：10.1016/j.tetlet.2012.11.051

  日期：2013.1

  and stereoselective procedure has been described for the synthesis of a series of β-enaminoesters and β-enaminones by vanadium(IV) acetylacetonate [VO(acac)2] catalyzed reaction of β-ketoesters and 1,3-diketones with both aliphatic and aromatic amines. X-ray crystallographic studies of some representative compounds corroborate two types of structural geometry formed by inter-molecular as well as intra-molecular

  已经描述了一种有效的立体选择性方法，该方法可通过乙酰丙酮钒（IV）[VO（acac）2 ]催化β-酮酸酯和1,3-二酮与脂肪族化合物的合成来合成一系列β-烯胺酯和β-烯酮和芳香胺。一些代表性化合物的X射线晶体学研究证实了分子间和分子内氢键形成的两种类型的结构几何形状。
• Visible Light Promoted β-C-H Alkylation of β-Ketocarbonyls <i>via</i> a β-Enaminyl Radical Intermediate
  作者：Dehong Wang、Long Zhang、Sanzhong Luo

  DOI：10.1002/cjoc.201700785

  日期：2018.4

  carbonyl activation mode is reported on the basis of photo‐induced single‐electron‐transfer (SET) oxidation of a secondary enamine. The resultant β‐enaminyl radical intermediate was trapped by a wide range of Michael acceptors, producing β‐alkylation products of β‐ketocarbonyls in a highly efficient manner.

  在仲烯胺的光诱导单电子转移（SET）氧化的基础上报道了5πe羰基活化模式。生成的β-烯丙基自由基中间体被多种Michael受体捕获，从而以高效方式生成β-酮羰基的β-烷基化产物。
• Ca(CF3COO)2: An efficient Lewis acid catalyst for chemo- and regio-selective enamination of β-dicarbonyl compounds
  作者：Mohamed Anoir Harrad、Rachid Outtouch、Mustapha Ait Ali、Larbi El Firdoussi、Abdallah Karim、Alain Roucoux

  DOI：10.1016/j.catcom.2009.11.019

  日期：2010.1

  A relevant procedure has been developed for the synthesis of β-enaminoesters catalysed by Ca(CF3COO)2. The reaction of β-ketoesters with primary amines was efficiently carried out under solvent-free conditions at room temperature and led to chemo- and regio-selective formations of enamine derivatives in high yields.

  已经开发了用于由Ca（CF 3 COO）2催化的β-烯氨基酯的合成的相关程序。β-酮酸酯与伯胺的反应在无溶剂条件下于室温下有效地进行，并导致高产率地形成烯胺衍生物的化学和区域选择性形成。
• Arynes and Cyclic Alkynes as Synthetic Building Blocks for Stereodefined Quaternary Centers
  作者：Elias Picazo、Sarah M. Anthony、Maude Giroud、Adam Simon、Margeaux A. Miller、K. N. Houk、Neil K. Garg

  DOI：10.1021/jacs.8b02875

  日期：2018.6.20

  stereodefined quaternary centers from reactions of arynes and related strained intermediates using β-ketoester-derived substrates. The conversion of β-ketoesters to chiral enamines is followed by reaction with in situ generated strained arynes or cyclic alkynes. Hydrolytic workup provides the arylated or alkenylated products in enantiomeric excesses as high as 96%. We also describe the one-pot conversion

  我们报告了一种使用β-酮酯衍生底物从芳烃和相关应变中间体的反应合成立体定义的四元中心的简便方法。β-酮酯转化为手性烯胺，然后与原位生成的应变芳炔或环炔反应。水解后处理可提供对映体过量高达 96% 的芳基化或烯基化产物。我们还描述了 β-酮酯底物一锅法转化为相应的对映体富集的 α-芳基化产物。计算显示了手性如何从 N 结合手性助剂转移到最终产品。这是手性亲核试剂捕获芳炔以设置新立体中心的首次理论研究。我们的方法为立体选择性β-酮酯芳基化/烯基化这一具有挑战性的问题提供了解决方案，并形成了四元中心。
• Heterocycle Formation through Aza-Annulation: Stereochemically Controlled Syntheses of (.+-.)-5-Epitashiromine and (.+-.)-Tashiromine
  作者：K. Paulvannan、John R. Stille

  DOI：10.1021/jo00086a009

  日期：1994.4

  N-alkylenamines, stabilized through conjugation with an electron-withdrawing group, undergo aza-annulation with acryloyl chloride to provide a convergent route for the construction of six-membered nitrogen heterocycles. In addition to enhancing the C-alkylation process of annulation relative to the competing N-acylation process, the electron withdrawing substituent controlled the regioselectivity of alkene formation in both the intermediate enamine and in the unsaturated lactam product. A variety of functional groups, which include -COMe, -COPh, -CO(2)R, -CONHPh, -CN, -P(O)(OEt)(2), and -SO(2)Ph, were used to determine the effect of the electron-withdrawing substituents upon both the annulation reaction with acryloyl chloride and the subsequent hydrogenation process. When the enamide annulation product was stabilized through conjugation with ester or amide substituents, catalytic hydrogenation of the ate-annulation product resulted in the formation of vicinal stereocenters with high cis selectivity. The utility of this methodology was demonstrated by application of the condensation/aza-annulation/hydrogenation sequence as the key for construction and stereochemical control of the indolizidine ring system of (+/-)-tashiromine.