关于aryl-C ((sp3) 键的亚tropisomerism:在大麻衍生物中的化学驱动的旋转路径
Clément Denhez1, Pedro Lameiras1, Hatice Berber1
1Université de Reims Champagne Ardenne, CNRS, ICMR UMR 7312, 51097 Reims, France. hatice.berber@univ-reims.fr.
Organic & biomolecular chemistry
|November 27, 2023
概括
这项研究研究了大麻二醇衍生物,揭示了围绕关键化学键键的有限旋转. 特定的修改影响过渡状态的稳定性,影响分子形状和性质.
科学领域:
- 有机化学 有机化学
- 计算化学的计算化学
- 频谱学是一种光谱学.
背景情况:
- Cannabidiol (CBD) 衍生物正在探索其独特的结构性质.
- 围绕单键的有限旋转可以导致稳定,不可叠加的镜像 (atropisomers).
- 了解形态动力学对于预测分子行为和设计新化合物至关重要.
研究的目的:
- 为了检查 ortho O 替代的纳夫甲基环素和纳夫甲基环素氧化物衍生物的结构性行为.
- 为了确定这些化合物中围绕C(sp2) -C(sp3) 轴的旋转障碍.
- 研究化学修饰对过渡状态的稳定性的影响.
主要方法:
- 使用可变温度核磁共振 (VT-NMR) 实验来研究形状变化.
- 密度函数理论 (DFT) 的计算被用来建模过渡状态和旋转路径.
- 对以前报告的衍生物进行了分析,以获得比较的见解.
主要成果:
- 通过在298K的旋转障碍在91.1到95.1kJmol-1之间的旋转障碍,成功合成了亚特罗皮索默性大麻二醇衍生物.
- 确定了两个不同的过渡状态 (TS1和TS2),相对稳定性取决于单烯环的修改.
- 纳基衍生物的旋转路径与基类似物的旋转路径相似,基环素的旋转速度比基环素的旋转速度慢.
结论:
- 这项研究阐明了新型大麻衍生物的结构动态,突出了结构修改对旋转障碍的影响.
- 这些发现提供了对这些系统中控制着体体的因素的见解,这与合成化学和药物设计有关.
- 对比分析证实了相关的芳香系统中保存的旋转机制,强调了计算方法的预测能力.
相关概念视频
Stereoisomerism of Cyclic Compounds
8.9K
In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...
8.9K
Isomerism in Alkenes
12.0K
Alkenes like 1-butene and 2-butene exhibit constitutional isomerism, as they differ in the position of the double bond. Further, 2-butene exhibits stereoisomerism and exists as two distinct compounds differing in spatial arrangement.
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
12.0K
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
4.6K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
4.6K
Disubstituted Cyclohexanes: cis-trans Isomerism
12.0K
Depending upon the different spatial orientation of the substituents, the disubstituted cycloalkanes exhibit two types of stereoisomers. The cis isomers have the substituents on the same side of the ring, whereas the trans isomers have the substituents on the opposite sides. These stereoisomers exhibit different physical properties and cannot be interconverted without breaking the carbon-carbon bonds.
In cyclohexane, the substituents can occupy different positions generating distinct isomers....
In cyclohexane, the substituents can occupy different positions generating distinct isomers....
12.0K
Naming Enantiomers
20.4K
The naming of enantiomers employs the Cahn–Ingold–Prelog rules that involve assigning priorities to different substituent groups at a chiral center. Each enantiomer, being a distinct molecule, is assigned a unique name by the Cahn–Ingold–Prelog (CIP) rules, also called the R–S system. The prefix R- or S- attached to the chiral centers in an enantiomer is dependent on the spatial arrangement of the four substituents on the chiral center. The R–S system...
20.4K
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
2.7K
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
2.7K

![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
