对于固态二烯光环添加的纯循环异构体的协调驱动的立体控制策略
Meng-Fan Wang1,2, Yan Mi2, Fei-Long Hu1,2
1College of Chemistry, Chemical Engineering and Materials Science , Soochow University , Suzhou 215123 , People's Republic of China.
Journal of the American Chemical Society
|December 25, 2019
概括
化学家现在可以使用一种新的协调相互作用策略来实现纯循环化合物. 这种方法精确地控制光环添加反应中的立体化学,消除不需要的同位素.
科学领域:
- 有机化学
- 摄影化学
- 超分子化学
背景情况:
- 光化学反应是重要的合成工具,但往往缺乏选择性,产生不必要的同位素副产品.
- 在光环添加反应中实现立体化学控制仍然是合成化学的一个重大挑战.
研究的目的:
- 在光环添加反应中开发一种用于精确立体化学控制的新合成策略.
- 通过基于协调的方法制造无副产品的纯同位素循环化合物.
主要方法:
- 采用了以协调互动为导向的合成策略.
- 通过协调相互作用固定反应物以控制它们的排列和配置.
- 对协调反应物进行光环添加反应.
主要成果:
- 提出的策略成功地实现了对同位素循环化合物的精确立体化学控制.
- 第一次,所有相关的光环添加产品都没有同位素副产品.
- 该方法在生产纯循环化合物方面具有很高的选择性和效率.
结论:
- 协调相互作用为光化学反应中的立体化学提供了强大的工具.
- 这项工作为合成纯循环化合物提供了一个新的,高度选择性的途径.
- 这项研究扩大了光环添加反应在有机合成中的用处.
相关概念视频
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
4.6K
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.
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[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
12.0K
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.
12.0K
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
5.3K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
5.3K
Cycloaddition Reactions: Overview
3.3K
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.
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Photochemical Electrocyclic Reactions: Stereochemistry
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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
2.1K
Thermal Electrocyclic Reactions: Stereochemistry
2.4K
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.
2.4K


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