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

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 H2 O2 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.

Keywords: hydroxylation of benzene; polyoxovanadates; quinolinium; supramolecular photocatalysis; synergistic catalysis.