Anderson-type polyoxometalate-based metal-organic framework as an efficient heterogeneous catalyst for selective oxidation of benzylic C-H bonds

Oxidative transformation of benzylic C-H bonds into functional carbonyl groups under mild conditions represents an efficient method for the synthesis of aromatic carboxylic acids and ketones. Here we report a high-efficiency catalyst system constructed from an Anderson-type polyoxometalate-based met...

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Bibliographic Details
Published in:RSC advances 2024-01, Vol.14 (1), p.364-372
Main Authors: Tan, Hong-Ru, Zhou, Xiang, Gong, Tengfei, You, Hanqi, Zheng, Qi, Zhao, Sheng-Yin, Xuan, Weimin
Format: Article
Language:English
Subjects:
Carbonyl groups
Carbonyls
Carboxylic acids
Catalysts
Chemical reactions
Chemistry
Ketones
Metal-organic frameworks
Oxidation
Polyoxometallates
Substrates
Synergistic effect
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Summary:Oxidative transformation of benzylic C-H bonds into functional carbonyl groups under mild conditions represents an efficient method for the synthesis of aromatic carboxylic acids and ketones. Here we report a high-efficiency catalyst system constructed from an Anderson-type polyoxometalate-based metal-Organic framework ( POMOF-1 ) and N -hydroxyphthalimide (NHPI) for selective oxidation of methylarenes and alkylarenes under 1 atm O 2 atmosphere. POMOF-1 exerted a synergistic effect originating from the well-aligned Anderson {CrMo 6 } clusters and Cu centers within the framework, and this entailed good cooperation with NHPI to catalyze the selective oxidation. Accordingly, the reactions exhibit good tolerance and chemical selectivity for a wide range of substrates bearing diverse substituent groups, and the corresponding carboxylic acids and ketones were harvested in good yields under mild conditions. Mechanism study reveals that POMOF-1 worked synergistically with NPHI to activate the benzylic C-H bonds of substrates, which are sequentially oxidized by oxygen and HOO&z.rad; to give rise to the products. This work may pave a way to design high-efficiency catalysts by integration of polyoxometalate-based materials with NPHI for challenging C-H activation. Self-assembly of Anderson-type polyoxometalate {CrMo 6 } with Cu 2+ and bistriazole L affords POMOF-1 that works cooperatively with NPHI for oxidative transformation of benzylic C-H bonds into carbonyl compounds.
ISSN:2046-2069
2046-2069
DOI:10.1039/d3ra07120k