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Highly efficient C–F bond cleavage to access esters over robust silicon-aluminum phosphate catalyst

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Abstract

Trifluoromethyl defluorination reaction plays a crucial role in promoting drug discovery, pesticide development and materials science. However, achieving C–F bond cleavage over heterogeneous catalysts remains a great challenge. Herein, we use methanol as the defluorocarbonylation reagent and silicon-aluminum phosphate mesoporous materials (named P–xSi–Al2O3, where x represents the Si–Al2O3 ratio) as the heterogeneous defluorination catalysts, successfully convert trifluorotoluene to methyl benzoate (Conv. 89.57%, Sel. 87.37%). Detailed investigations revealed that the acidity as well as the Lewis/Brønsted acid site of the catalyst promote the defluorination process. Meanwhile, the mesoporous structure of sheet-like fibers makes active sites easier to access the substrates, which results in an excellent performance. The defluorination reaction can be realized without solvent, noble metal and excessive acid additives over the present catalytic system and the good substrate universality in the carbonylation reaction of halogen-containing aromatic hydrocarbons reveal great potential for practical dehalogenation and carbonylation reaction.

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All data analyzed or generated during this work are included in this manuscript and its supporting information file. The supporting information including different experimental conditions, SEM images, XRD spectra, reused catalysts images and GC–MS figures, etc.

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Acknowledgements

This work is supported by Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology (No.2017E10001), Zhejiang Province (China).

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Authors and Affiliations

  1. Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China

    Menglu Cai, Xiaoguang Zhang, Haoqiong Zhu, Xiaozhong Wang, Yingqi Chen & Liyan Dai

  2. Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou, 310027, China

    Menglu Cai

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Contributions

Menglu Cai performed investigation, formal analysis, methodology, writing—original draft; Xiaoguang Zhang provided investigation, formal analysis, methodology, data curation, writing—review & editing; Haoqiong Zhu did investigation and writing—review & editing; Xiaozhong Wang presented visualization and resources; Yingqi Chen developed resources; Liyan Dai conducted supervision, resources, and writing—review & editing.

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Correspondence to Liyan Dai.

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Cai, M., Zhang, X., Zhu, H. et al. Highly efficient C–F bond cleavage to access esters over robust silicon-aluminum phosphate catalyst. J Mater Sci 59, 1896–1913 (2024). https://doi.org/10.1007/s10853-024-09337-6

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