A magnetic nanocatalyst based on Bronsted acid and Lewis acid centers for the efficient synthesis of polycyclic melting 1,5-benzodiazepines

Abstract

In this study, 3-(Triethoxysilyl)propyl chloride (CPTES) was used to modify the surface of magnetic nanoparticles Fe3O4@SiO2, and aminomethylphosphonic acid (AMPA) was further anchored on the surface. Then, Ce (III) was used as the ligand to immobilize the surface of the modified material with N/O as the donor. Magnetic nanocatalysts (Fe3O4@SiO2@CPTES@AMPA@CeCl3) were successfully prepared. The prepared catalysts were characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen absorption-desorption experiment (BET), vibrating sample magnetometer (VSM), energy dispersive spectroscopy (EDS) and inductively coupled plasma atomic emission spectrometry (ICP-AES). A synergetic effect of Brønsted and Lewis acid (AMPA and CeCl3) of the magnetic nanocatalyst was examined to active carbonyl, imine or enamine bonds for the synthesis of polycyclic fused 1,5-benzodiazepine with quaternary carbon centers or quinoxaline ring in a one-pot method. It was found that this catalyst exhibited excellent catalytic activities (TON up to 111368, TOF up to 110232 h−1) and high selectivities in the synthesis of fused 1,5-benzodiazepine compounds (22 examples, 85–96 % yields). The mechanism for the synthesis of polycyclic fused 1,5-benzodiazepine catalyzed by Fe3O4@SiO2@CPTES@AMPA@CeCl3 was proposed. The nanocatalyst was readily recovered by simple magnetic decantation and can be recyclable without obviously reducing catalytic activity up to seven times.