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Earth-Abundant Heterogeneous Cobalt Catalyst for Selective Ring Hydrogenation of (Hetero)arenes and Gram-Scale Synthesis of Pharmaceutical Intermediates
B. Singh, V. Goyal, D. Sarma, R. Kumar, T. Bhatt, , C. Raji Reddy, A. Narani,
Published in American Chemical Society
2023
Pages: 9724 - 9744
Abstract
It is highly desired but scientifically as well as technologically challenging to develop non-noble metal-based hydrogenation catalysts that can substitute noble metal-based ones. Herein, we present a facile and environmentally friendly approach for synthesizing pine needle biomass-derived nitrogen-doped carbon-supported Co3O4 nanoparticles (Co3O4/PNC). The whole process involves the impregnation of pine needles with cobalt nitrate salt and subsequent pyrolysis at 500 °C under a nitrogen atmosphere. Applying this Co3O4/PNC nanocatalyst, a broad range of substituted phenols and functional organic chemicals, including N- and O-heteroarenes, could be efficiently transformed into their corresponding ring-hydrogenated products in good-to-excellent yields (>55 examples). In addition, this catalytic approach has proved useful for the preparation of seven key drug intermediates on a gram scale, which are commonly used in manufacturing active pharmaceutical ingredients in bulk quantities. Advantageously, cyclohexanecarboxylic acid, a key pharmaceutical building block of praziquantel, was synthesized from polystyrene in a two-step process. The pivotal physicochemical properties of fresh and spent Co3O4/PNC nanocatalysts were thoroughly investigated by high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, N2 adsorption-desorption, Raman analysis, H2-temperature programmed reduction, and CO2-temperature-programmed desorption analysis. The cobalt content in the Co3O4/PNC nanocatalyst was estimated by inductively coupled plasma atomic emission spectroscopy analysis. Besides, the Co3O4/PNC nanocatalyst is stable, easily recovered, and reused effectively for four catalytic cycles with no loss of activity or selectivity. Furthermore, density functional theory calculations were performed to get more insights into the reaction mechanism. © 2023 American Chemical Society.
About the journal
JournalACS Catalysis
PublisherAmerican Chemical Society
ISSN21555435