功能化异构素的合作捕获合成――化学范围,动力学和机制研究
Faustine d'Orchymont1, Jason P Holland1
1Department of Chemistry, University of Zurich, Winterthurerstrasse 190, Zurich CH-8057, Switzerland.
Journal of the American Chemical Society
|June 5, 2023
概括
这项研究详细介绍了如何使用β-环氧的各种功能组来修改分子互锁的分子,特别是异氧. 这项研究可以为医学创造先进的超分子工具.
科学领域:
- 超分子化学
- 有机合成
- 化学生物学
背景情况:
- 分子互锁的分子,如异质素,有望用于医学应用.
- 这些结构的功能化对于开发向药物和成像剂至关重要.
研究的目的:
- 为了研究β-cyclodextrin (β-CD) 衍生物化在cucurbit[6]uril (CB[6]) 介导的异构合成中的化学范围.
- 为了进一步功能化,识别与有效的轮素形成相容的β-CD上的反应组.
主要方法:
- 合成了9种具有多种功能群的β-CD衍生物 (托西酸盐,氨基,碳酸,亚酸,阿尼林,异酸).
- 在 hetero[4]rotaxanes 的合作捕获合成中评估了这些衍生物.
- 结合实验动力测量与密度函数理论 (DFT) 计算研究.
主要成果:
- 在不影响合成效率的情况下,已确定可成功纳入异构素的特定β-CD衍生物.
- 阐明了合作捕获过程的机械路径和速度决定的步骤.
- 计算分析显示β-CD和CB[6]的相互作用增强了轮素形成率和效率.
结论:
- 通过β-CD衍生建立了通过β-CD衍生功能化的合成范围.
- 证明了解合作捕获机制有助于开发先进的功能化轮素.
- 这项工作为生物医学中 hetero[4]rotaxanes 的更广泛应用铺平了道路.
![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)
相关概念视频
02:36Regioselectivity and Stereochemistry of Hydroboration
8.2K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.2K
01:16Cycloaddition Reactions: Overview
2.7K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
2.7K
01:17Thermal Electrocyclic Reactions: Stereochemistry
2.1K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.1K
01:26Thermal and Photochemical Electrocyclic Reactions: Overview
2.4K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.4K
01:12Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.1K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.1K
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.4K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.4K