1-(3-甲基-丁-1-烯基)-吡咯烷 | 55023-48-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 中文名称: 1-(3-甲基-丁-1-烯基)-吡咯烷
• 英文名称: 1-(3-methyl-but-1-enyl)-pyrrolidine
• 英文别名: pyrrolidino-3-methylbut-1-ene；1-(3-Methylbut-1-en-1-yl)pyrrolidine；1-(3-methylbut-1-enyl)pyrrolidine
• CAS: 55023-48-8
• 化学式: C₉H₁₇N
• 分子量: 139.241
• InChiKey: BVLGEIBZZYTZKC-UHFFFAOYSA-N

物化性质

• 沸点：
  194.8±7.0 °C(Predicted)
• 密度：
  0.934±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(3-甲基-丁-1-烯基)-吡咯烷 生成 5-异丙基-2-甲基-2-环己烯-1-酮
  参考文献：
  名称：

  An alkylative 1,2-carbonyl transposition of 2-methoxy-2-cyclohexenones

  摘要：

  DOI：

  10.1021/jo01331a021
• 作为产物：
  描述：

  异戊醛 以 氘代二甲亚砜 、 氘代苯 为溶剂， 生成 1-(3-甲基-丁-1-烯基)-吡咯烷
  参考文献：
  名称：

  Importance of the Electron Correlation and Dispersion Corrections in Calculations Involving Enamines, Hemiaminals, and Aminals. Comparison of B3LYP, M06-2X, MP2, and CCSD Results with Experimental Data

  摘要：

  While B3LYP, M06-2X, and MP2 calculations predict the Delta G degrees values for exchange equilibria between enamines and ketones with similar acceptable accuracy, the M06-2X/6-311+G(d,p) and MP2/6-311+G(d,p) methods are required for enamine formation reactions (for example, for enamine 5a, arising from 3-methylbutanal and pyrrolidine). Stronger disagreement was observed when calculated energies of hemiaminals (N,O-acetals) and aminals (N,N-acetals) were compared with experimental equilibrium constants, which are reported here for the first time. Although it is known that the B3LYP method does not provide a good description of the London dispersion forces, while M06-2X and MP2 may overestimate them, it is shown here how large the gaps are and that at least single-point calculations at the CCSD(T)/6-31+G(d) level should be used for these reaction intermediates; CCSD(T)/6-31+G(d) and CCSD(T)/6-311+G(d,p) calculations afford Delta G degrees values in some cases quite close to MP2/6-311+G(d,p) while in others closer to M06-2X/6-311+G(d,p). The effect of solvents is similarly predicted by the SMD, CPCM, and IEFPCM approaches (with energy differences below 1 kcal/mol).

  DOI：

  10.1021/acs.joc.5b01814

文献信息

• Transfer of 1-Alkenyl Groups between Secondary Amines. Relative Stability and Reactivity of Enamines from Popular Organocatalysts
  作者：Héctor Carneros、Dani Sánchez、Jaume Vilarrasa

  DOI：10.1021/ol501044u

  日期：2014.6.6

  Enamines from 3-methylbutanal and several Pro- and Phe-derived secondary amines were prepared in DMSO-d6, CD3CN, and CDCl3. For the first time, the relative thermodynamic stabilities of these and other enamines were compared, and rapid exchanges of 1-alkenyl groups were demonstrated. Competition experiments showed that the most favored enamines (without significant steric inhibition of resonance) react

  在DMSO- d 6，CD 3 CN和CDCl 3中制备了3-甲基丁醛的烯胺以及几种Pro和Phe衍生的仲胺。第一次，比较了这些和其他烯胺的相对热力学稳定性，并证明了1-烯基的快速交换。竞争实验表明，最喜欢的烯胺（对共振没有明显的空间抑制作用）与亲电子试剂反应更快。
• 一种隐酮的合成方法
  申请人：天津市安凯特科技发展有限公司

  公开号：CN110590523A

  公开（公告）日：2019-12-20

  本发明提供了一种隐酮的合成方法，其特征在于：包括采用四氢吡咯和异戊醛反应合成烯胺的步骤；采用烯胺和丁烯酮反应生成中间体2‑异丙基‑5‑己醛的步骤；水洗后的含2‑异丙基‑5‑己醛的有机相在有水的碱性条件下，回流2‑6h进行环化反应，然后经水洗，回收溶剂减压蒸馏得到隐酮粗品的步骤。本发明所述的隐酮的合成方法，采用四氢吡咯作为反应物之一，由于其沸点低，容易回收，且工艺条件简单，流程短，收率高，易于实现工业生产。
• Direct Enantioselective Organocatalytic Hydroxymethylation of Aldehydes Catalyzed by α,α-Diphenylprolinol Trimethylsilyl Ether
  作者：Robert K. Boeckman、John R. Miller

  DOI：10.1021/ol9017479

  日期：2009.10.15

  The direct enantioselective hydroxymethylation of aldehydes utilizing α,α-diphenylprolinol trimethylsilyl ether as an organocatalyst is described. The intermediate α-substituted β-hydroxyaldehydes were not isolated but converted to the more readily isolable derivatives. For example, the derived hydroxy acids were isolated in up to 94% yield with excellent enantioselectivity.

  描述了利用α，α-二苯基脯氨醇三甲基甲硅烷基醚作为有机催化剂的醛的直接对映选择性羟甲基化。没有分离出中间体α-取代的β-羟基醛，而是将其转化为更容易分离的衍生物。例如，以优异的对映选择性以高达94％的收率分离出衍生的羟基酸。
• Synthesis of an Oxazole–Pyrrole–Piperazine Scaffold as an α-Helix Mimetic
  作者：Lionel Moisan、Severin Odermatt、Naran Gombosuren、Alexandre Carella、Julius Rebek

  DOI：10.1002/ejoc.200701164

  日期：2008.4

  The synthesis of nonpeptidic α-helix mimetics based on a tricyclic oxazole–pyrrole–piperazine scaffold is described. The scaffold presents both a hydrophobic surface for recognition and a hydrophilic edge that enhances solubility. The synthesis is highly modular and allows the targeting of a range of protein–protein interactions involving α-helices. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  描述了基于三环恶唑-吡咯-哌嗪支架的非肽类 α-螺旋模拟物的合成。支架呈现出用于识别的疏水表面和增强溶解性的亲水边缘。合成是高度模块化的，并允许靶向一系列涉及 α-螺旋的蛋白质-蛋白质相互作用。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Phosphoric Acid Catalyzed Desymmetrization of Bicyclic Bislactones Bearing an All-Carbon Stereogenic Center: Total Syntheses of (−)-Rhazinilam and (−)-Leucomidine B
  作者：Jean-Baptiste Gualtierotti、Delphine Pasche、Qian Wang、Jieping Zhu

  DOI：10.1002/anie.201405842

  日期：2014.9.8

  the presence of a catalytic amount of an imidodiphosphoric acid, enantioselective desymmetrization of bicyclic bislactones by reaction with alcohols took place smoothly to afford enantiomerically enriched monoacids having an all‐carbon stereogenic center. Concise catalytic enantioselective syntheses of both (−)‐rhazinilam and (−)‐leucomidine B were subsequently developed using (S)‐methyl 4‐ethyl‐4‐formylpimelate

  在催化量的亚氨基二磷酸存在下，通过与醇的反应，双环双内酯的对映选择性去对称化反应顺利进行，从而得到具有全碳立体异构中心的对映异构体富集的单酸。随后，使用（S）-4-甲基-4-乙基-4-甲酰基甲基吡啶甲酸单酸酯作为常见的起始原料，开发了（-）-rhazinilam和（-）-leucomidine B的简明催化对映选择性合成。