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喹啉鎓和基于多氧钒酸盐的超分子催化剂光诱导苯高效羟基化制苯酚

Light-Induced Efficient Hydroxylation of Benzene to Phenol by Quinolinium and Polyoxovanadate-Based Supramolecular Catalysts.

作者信息

Gu Yaqi, Li Qi, Zang Dejin, Huang Yichao, Yu Han, Wei Yongge

机构信息

Key Lab of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Haidian District, Beijing, 100084, P. R. China.

State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing, 100191, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2021 Jun 7;60(24):13310-13316. doi: 10.1002/anie.202011164. Epub 2020 Oct 15.

Abstract

Direct Hydroxylation of benzene to phenol with high yield and selectivity has been the goal of phenol industrial production. Photocatalysis can serve as a competitive method to realize the hydroxylation of benzene to phenol owing to its cost-effective and environmental friendliness, however it is still a forbidding challenge to obtain good yield, high selectivity and high atom availability meanwhile. Here we show a series of supramolecular catalysts based on alkoxohexavanadate anions and quinolinium ions for the photocatalytic hydroxylation of benzene to phenol under UV irradiation. We demonstrate that polyoxoalkoxovanadates can serve as efficient catalysts which can not only stabilize quinolinium radicals but also reuse H O produced by quinolinium ions under light irradiation to obtain excellent synergistic effect, including competitive good yield (50.1 %), high selectivity (>99 %) and high atom availability.

摘要

将苯直接羟基化为苯酚并具有高收率和选择性一直是苯酚工业生产的目标。光催化由于其成本效益高和环境友好性,可作为实现苯羟基化为苯酚的一种有竞争力的方法,然而,同时获得高收率、高选择性和高原子利用率仍然是一个艰巨的挑战。在此,我们展示了一系列基于烷氧基六钒酸根阴离子和喹啉鎓离子的超分子催化剂,用于在紫外光照射下将苯光催化羟基化为苯酚。我们证明,聚氧烷氧基钒酸盐可以作为高效催化剂,不仅可以稳定喹啉鎓自由基,还可以在光照下再利用喹啉鎓离子产生的H₂O,以获得优异的协同效应,包括具有竞争力的高收率(50.1%)、高选择性(>99%)和高原子利用率。

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