一个固体非共价有机双螺旋框架催化了不对称的 [6 + 4] 循环添加
Tianyu Zheng1, Nils Nöthling1, Zikuan Wang1
1Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim an der Ruhr, Germany.
概括
化学家们从非共价有机框架中开发出一种新的双螺旋形催化剂. 这种催化剂使具有挑战性的 [6 + 4] 循环添加成为可能,为有价值的 10 个环提供了新的途径.
科学领域:
- 有机化学
- 催化剂
- 超分子化学
背景情况:
- [4 + 2] 循环添加是一种多功能合成工具.
- 控制 [6 + 4] 循环添加的反应性和选择性仍然是一个重大挑战.
- 通过循环加法获得10个环是有价值的,但很困难.
研究的目的:
- 为 [6 + 4] 循环加法开发一种通用和选择性的方法.
- 探索新型二胺基衍生框架的催化潜力.
- 从简单的基质中合成复杂的10个环结构.
主要方法:
- 设计和合成高酸度的二化物催化剂.
- 观察自发沉到双螺旋形的非共价有机框架 (COF).
- 使用不溶性COF作为 [6 + 4] 循环添加的异质催化剂.
主要成果:
- 不溶性COF催化剂在 [6 + 4]循环添加中表现出高反应性和立体选择性.
- 这种反应涉及简单的二烯和热,产生了10个环.
- 使用前体 imidodiphosphorimidate 的同质催化没有成功.
结论:
- 胺基二胺酸衍生COF可以作为有效的异质催化剂来挑战 [6 + 4] 循环添加.
- 这项工作介绍了一种新型的催化系统,用于构建具有高选择性的10个环.
- 一个分子前体的反应框架的自组装在催化中提供了一个新的策略.
相关概念视频
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Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
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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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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.
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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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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.
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Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
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Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
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