Primary amine–thiourea grafted graphene–based heterogeneous chiral catalysts for highly enantioselective Michael additions

Abstract

Heterogeneous asymmetric catalysis based on earth-abundant carbon materials put together the advantages for the ease of separation, simple regeneration, and high stability of solid catalysts as well as acts as low-cost, environmentally friendly metal-free alternative to the metal-based catalysts. Two new bifunctional carbocatalysts [(S,S) and (R,R) GO-PATU] were prepared by anchoring enantiomerically pure organosilanes bearing primary amine and thiourea groups to the graphene oxide (GO) skeleton covalently via silane coupling reaction. The surface modification of GO was analyzed by a combination of Fourier-transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron spectroscopy (TEM) techniques. The catalytic performances of graphene-based materials were investigated in the asymmetric Michael addition reactions of α,α-disubstituted-aldehydes to nitrostyrenes and N-substituted-maleimides. The effects of solvents and Brønsted basic or acidic additives were evaluated using both catalysts and good yields (up to 85%) and stereoselectivities (up to 95% ee) were obtained in dichloromethane at room temperature in the presence of l- and d-camphorsulfonic acid. Besides, recycling and reusing studies of the catalysts were successfully performed.