羟基芳醛在超高效无金属光催化 E→Z 烯烃异构化中的应用。

IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
ChemSusChem Pub Date : 2024-11-05 DOI:10.1002/cssc.202401387
Chun-Xiu Liu, Yao Yao, Zi-Wen Zhou, Song Qin, Zhi-Peng Yu, Fei-Yan Tao, Wen-Dian Li, Xiao-Qi Yu, Na Wang
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引用次数: 0

摘要

最近,光催化烯烃 E→Z 异构化以获得热力学稳定性较低的 Z-烯烃的策略受到了广泛关注。在这里,我们发现了一种羟基芳香醛敏化剂,它能在蓝光照射下快速实现烯烃的 E→Z 异构化。值得注意的是,2-羟基苯-1,3,5-三甲醛在蓝光辅助下可在短短 5 分钟内实现高效和选择性转化(Z/E=92:8)。该反应可成功放大到克级,并对肉桂酸乙酯的各种衍生物(27 个实例)和其他烯烃具有显著的反应活性。此外,前者可直接通过羟基衍生物环化生成 4-取代香豆素。这种方法具有无金属、高效、方便、无副产物和高选择性等突出优点。敏化剂三重态能量(ET)的相关性和初步的机理实验表明,该反应的完成是基于选择性激发机制。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Application of Hydroxyaromatic Aldehydes in Ultra-Efficient and Metal-Free Photocatalytic E→Z Isomerization of Olefin.

The strategy of photocatalyzed E→Z isomerization of olefins to access thermodynamically less stable Z-alkenes has recently received considerable attention. Here, we have discovered a sensitizer of hydroxyaromatic aldehyde that can rapidly achieve olefin E→Z isomerization under blue light irradiation. Notably, 2-hydroxybenzene-1,3,5-tricarbaldehyde, when assisted by blue light, can achieve efficient and selective conversion within just 5 minutes (Z/E=92 : 8). The reaction can be successfully scaled up to gram scale, and exhibits remarkable reactivity toward various derivatives of ethyl cinnamate (27 examples) and other olefins. Furthermore, the former can be directly cyclized by a hydroxyl derivative to produce 4-substituted coumarin. The prominent preponderance of this method includes being metal-free, efficient, convenient, no by-products and achieving high selectivity. Correlation of sensitizer triplet energy (ET) and preliminary mechanistic experiments indicate that the accomplishment of this reaction is based on the selective excitation mechanism.

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来源期刊
ChemSusChem
ChemSusChem 化学-化学综合
CiteScore
15.80
自引率
4.80%
发文量
555
审稿时长
1.8 months
期刊介绍: ChemSusChem Impact Factor (2016): 7.226 Scope: Interdisciplinary journal Focuses on research at the interface of chemistry and sustainability Features the best research on sustainability and energy Areas Covered: Chemistry Materials Science Chemical Engineering Biotechnology
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