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

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.