Magnetically recoverable nickel-palladium alloy nanocatalysts for direct C-H arylation reactions.

Novel magnetically recoverable nanocatalyst comprising nickel-palladium (NiPd) alloy nanoparticles (NPs) supported on reduced graphene oxide (rGO) modified with cobalt ferrite (CoFe2O4) NPs was fabricated for the direct C–H arylation of imidazopyridine, imidazole, indolizine and furan with aryl halides. To prepare the presented catalyst, rGO nanosheets were first modified with as-synthesized CoFe2O4 NPs and then the obtained CoFe2O4-rGO nanocomposites served as a support material for the synthesis of bimetallic NiPd alloy NPs at various compositions. The obtained CoFe2O4-rGO/NiPd nanocatalysts were characterized by many advanced analytical techniques including TEM, STEM-EDS, XRD, XPS, and ICP-MS. Next, to optimize the reaction conditions, CoFe2O4-rGO/NiPd nanocatalysts with different alloy compositions and their monometallic counterparts (CoFe2O4-rGO/Ni and CoFe2O4-rGO/Pd) were initially tested in the direct C–H arylation of imidazopyridine with bromobenzene. Among all tested nanocatalysts under the optimum reaction conditions, CoFe2O4-rGO/Ni20Pd80 showed the best catalytic activity in terms of the isolated product yields. The C–H arylation reactions were studied over a broad substrate scope (35 examples from 36 substrates) and gave the related biaryl products in good to excellent yields. Besides a broad substrate scope, the late-stage C–H arylation of zolimidine, a gastroprotective drug, was realized under the optimized reaction conditions. Moreover, the CoFe2O4-rGO/Ni20Pd80 nanocatalysts were recovered from the reaction medium using a simple magnet and reused in the C–H arylation reactions up to five consecutive runs without a significant drop in the product yield. This study shows that magnetically recoverable Pd nanoalloys are promising heterogeneous catalysts to be used in sustainable C–H functionalization reactions.