Au3+/Au0 Supported on Chromium(III) Terephthalate Metal Organic Framework (MIL-101) as an Efficient Heterogeneous Catalystfor Three-Component Coupling Synthesis of Propargylamines

Abstract

Post-synthesis modification is a useful method for the functionalization of metal-organic frameworks (MOFs). A novel catalyst Au@MIL-101-ED-SA (ED = ethylenediamine, SA = salicylaldehyde), containing coexisting Au³⁺ ions and Au⁰ nanoparticles, was prepared successfully by post-synthesis modification with ethylenediamine, salicylaldehyde and gold. Gold nanoparticles supported on MIL-101 (Au@MIL-101) were prepared successfully by the impregnation method. Au@MIL-101-ED-SA and Au@MIL-101 were characterized by N₂ adsorption-desorption, X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and inductively coupled plasma-optical emission spectrometry. Au@MIL-101-ED-SA and Au@MIL-101 were applied as environmentally friendly catalysts in the three-component coupling reaction of aldehydes, amines, and alkynes for the preparation of diverse propargylamines. Au@MIL-101-ED-SA contained a fraction of cationic gold (Au³⁺/Au⁰ = 0.9) and showed higher catalytic activity than Au@MIL-101, which was prepared by the impregnation method. Furthermore, the reactions were performed under heterogeneous conditions and the novel catalyst was successfully recycled for four consecutive runs.