Effective and selective direct aminoformylation of nitroarenes utilizing palladium nanoparticles assisted by fibrous-structured silica nanospheres

Palladium nanoparticles (~ 1–3 nm, 0.4 wt% Pd) were uniformly distributed over the surface of fibrous silica nanospheres (KCC-1) modified via aminopropyltriethoxysilane using a fast and cost-effective palladium (II) chloride reduction process. The Pd nanoparticles (Pd NPs) distribution over the ensuing catalyst Pd/KCC-1-NH 2 showed much more uniform distribution, and smaller size compared with the tedious hydrothermal reduction method. The morphological, chemical, and size analyses of Pd/KCC-1-NH 2 by BET, UV–Vis spectra, XRD, HR-TEM, EDS and XPS analysis revealed that the succeeding material consist of a distinct fibrous silica nanospheres support adorn with Pd NPs. The resultant nanocatalyst was tested for the one-step reductive aminoformylation of aromatic nitro compounds using formic acid. A wide range of substituted nitroarenes including electron withdrawing, releasing, sterically hindered and multifunctional groups have been converted to corresponding aryl formamide in quantitative yields (yields up to 98%) at moderate temperature (70 °C). Optimization study has proved that the 6 equivalent of formic acid is required and toluene was found to be the better solvent. The established practice is beneficial due to the use of formic acid as H 2 source and formylating agent, easiness in handling of the catalyst and simple workup procedure with efficient catalyst reusability. Graphic abstract