立体特异光化学环扩张化胺的化胺
Jonathan Clayden1, Faye E Knowles, Christel J Menet
1Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK. j.p.clayden@man.ac.uk
Journal of the American Chemical Society
|August 2, 2003
概括
研究人员开发了一种新型反应,其中N-基胺转化为诺卡拉迪因或循环乙. 这种环膨胀反应对奇拉胺胺具有很高的立体特异性,提供了新的合成途径.
科学领域:
- 有机化学 有机化学
- 摄影化学的使用.
- 合成方法论 合成方法论
背景情况:
- 胺是多功能有机化合物.
- 环膨胀反应对于合成复杂的循环结构至关重要.
- 光化学反应为分子转变提供了独特的途径.
研究的目的:
- 为了研究N-基胺的转化.
- 为了探索诺卡拉迪因和循环乙二烯的形成.
- 了解这种新奇反应的立体化学结果.
主要方法:
- 用LDA或t-BuLi等强基对N-基胺的处理.
- 使用 500 瓦灯进行辐射.
- 基于替代模式的反应产物的分析.
主要成果:
- 通过N-基组插入形成诺卡拉迪因或环二.
- 在奇拉本扎米德的环扩张中观察到高立体特异性.
- 反应通过一种涉及 pericyclic 反应和 dearomatizing cyclization 的拟议机制进行.
结论:
- 来自N-基胺的诺卡拉迪因和循环乙二烯的新合成途径已经建立.
- 反应表现出优异的立体化学控制,特别是与性基质.
- 这些发现提供了关于有机合成中光化学和热再排列的机制性途径的见解.
相关概念视频
¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)
When proton-coupled carbon-13 spectra are simplified by a broadband proton decoupling technique, structural information about the coupled protons is lost. Distortionless enhancement by polarization transfer (DEPT) is a technique that provides information on the number of hydrogens attached to each carbon in a molecule. While the DEPT experiment utilizes complex pulse sequences, the pulse delay and flip angle are specifically manipulated. The resulting signals have different phases depending on...
IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations
Identical bonds within a polyatomic group can stretch symmetrically (in-phase) or asymmetrically (out-of-phase). Similar to hydrogen bonding, these vibrations also influence the shape of the IR peak. Generally, asymmetric stretching frequencies are higher than symmetric stretching frequencies. For example, primary amines exhibit two distinct IR peaks between 3300–3500 cm−1 corresponding to the symmetric and asymmetric N-H stretching, while secondary amines exhibit a single stretching vibration...
Mass Spectrum
A mass spectrum is the graphical representation of the relative abundance of the charged fragments in an analyte plotted against their mass-to-charge ratio (m/z). The plot's x-axis represents the ratio of the mass of the charged fragment to the number of charges it carries. The y axis of the plot represents the relative abundance of each charged species. The relative abundance is calculated from the signal intensity of each charged species recorded at the detector. The most intense signal (the...
Chemical Ionization (CI) Mass Spectrometry
The molecular ion peak of a molecule in the mass spectrum provides vital information for molecular identification. However, conventional electron impact ionization can lead to the rapid dissociation of some molecular ions before they reach the detector. A milder ionization method is required to increase the lifetime of such ionized analyte molecules. Chemical ionization (CI) is a gas-phase protonation reaction useful for mass-analyzing analyte molecules that are easily protonated to yield the...
Mass Spectrometry: Alkyl Halide Fragmentation
Chlorine isotopes exist as 35Cl and 37Cl in a 3:1 ratio, while bromine isotopes exist as 79Br and 81Br in a 1:1 ratio. The mass spectrum of alkyl halides typically produces two distinct molecular ion peaks, the molecular ion peak, [M], and the molecular ion plus two, [M + 2] peak. The relative heights of these two peaks are proportional to the isotopic abundance ratios of the halide. For example, 2‐chloropropane and 1‐bromopropane display two peaks with relative peak heights in a 3:1 and 1:1...
Variables Affecting Phosphorescence and Fluorescence
Fluorescence and phosphorescence are essential phenomena in fields like analytical chemistry, biological imaging, and materials science, where they detect molecular properties and visualize cellular structures. Understanding the variables that influence these luminescent behaviors is crucial for maximizing accuracy and efficiency in their applications. These variables can broadly be grouped into chemical structure, solvent properties, and external conditions, each playing a distinct role in...


