五/六个成员循环乙烯的碳诱导环开反应:扩大功能组引入和分子结构构建的边界
Jun Xiao1,2, Dandan Jiang1,2, Xiujuan Wu2
1Jiangxi Provincial Key Laboratory of Functional Crystalline Materials Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi Province, P.R. China. liukunming@jxust.edu.cn.
Organic & biomolecular chemistry
|January 22, 2025
概括
碳诱导的环开放反应为从循环中构建复杂分子提供了新的途径. 本综述详细介绍了20年来碳烯前体和形成途径的进展.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 循环以太是复杂分子的多功能构建块.
- 环开放反应是功能化的关键,但对于低应变环来说具有挑战性.
- 像酸催化剂这样的传统方法也有局限性.
研究的目的:
- 审查循环乙烯的碳烯诱导环开放反应的演变.
- 突出碳基前体和形成机制方面的进展.
- 为开发新型碳源和氧中间体提供见解.
主要方法:
- 在过去的二十年里,对卡尔诱导的环开反应的文献的综述.
- 对碳烯前体及其形成途径的分析.
- 检查氧中间体的形成和反应性.
主要成果:
- 碳诱导的通路扩大了循环开环的选择性.
- 开发了新的碳烯前体和形成方法.
- 了解氧中间体的形成对于反应控制至关重要.
结论:
- 碳诱导的环开放代表了循环以太功能化的重大进步.
- 对碳化合物化学的持续研究将推动合成方法的创新.
- 这一综述为未来在该领域的发现提供了基础.
相关概念视频
Base-Catalyzed Ring-Opening of Epoxides
8.2K
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
8.2K
Acid-Catalyzed Ring-Opening of Epoxides
7.1K
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
7.1K
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
3.7K
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
3.7K
Thermal Electrocyclic Reactions: Stereochemistry
2.0K
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.
2.0K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
10.0K
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
10.0K
Structure and Nomenclature of Epoxides
6.3K
Cyclic ethers are heterocyclic compounds with an oxygen atom in the ring along with carbon atoms. They are named depending on the number of carbon atoms present in their ring system. Cyclic ethers with a three-membered ring system are called “oxirane”, four-membered ring systems as “oxetane”, five-membered ring systems as “oxolane”, and six-membered ring systems as “oxane”. The cyclic structure of these rings imposes angle strain, and this strain...
6.3K


![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)