Palladium nanoparticle biosynthesis via Yerba Mate (Ilex paraguariensis) extract: an efficient eco-friendly catalyst for Suzuki–Miyaura reactions

Abstract

This manuscript relates, for the first time, palladium nanoparticle production by bio-reduction using an Ilex paraguariensis aqueous extract. The solid obtained, PdISM, was used as a catalyst in Suzuki–Miyaura cross-coupling, composing a new eco-friendly, ligand-free, and low cost catalytic system. Excellent yields were obtained in the coupling of aryl iodides and bromides with phenylboronic acid. The same catalyst load was able to be recycled 3x. Graphical Abstract

New sustainable and robust catalytic supports for palladium nanoparticles generated from chitosan/cellulose film and corn stem biochar

“…The results presented in Table 2 show that both developed catalysts were successful in the studied reaction (entries 7 and 8), characterizing sustainable catalytic systems as they do not require phosphine ligands and/or quaternary ammonium salts, in addition to employing eco-friendly reagents (ethanol and K 2 CO 3 ). In this sense, the pair K 2 CO 3 /ethanol (base/solvent) proved to be the most efficient in terms of reaction yield, corroborating previous works by our research group (Rosa et al 2019 ; Schmitt et al 2021 ). On the other hand, the nonpolar solvent dioxane and the organic base NEt 3 did not provide the maximum catalytic activity of the catalysts tested (entries 1–6).…”

“…Although the result is minimal, biphenyl was obtained by direct reaction and no evidence of homocoupling of PhB(OH) 2 was encountered. In this study, TON and TOF values were calculated and the Pd@CSB catalyst proved to be superior in terms of TOF values (see entries 4 and 6) to other catalytic systems that employ similar conditions (conventional heating and the same amount of catalyst) (Faria et al 2014 ; Rosa et al 2019 ; Schmitt et al 2021 ).…”

“…Having both solids (Pd/CCF and Pd@CSB) characterized, the Suzuki-Miyaura reaction between phenylboronic acid and 4-bromobenzonitrile was chosen to optimize the catalytic systems (Scheme 1 ; Table 2 ). For this purpose, bases and solvents were varied based on previous works of our research group and the use of the eco-friendly reagents was prioritized (Faria et al 2014 ; Rosa et al 2019 ; Schmitt et al 2021 ).

Scheme 1 The Suzuki-Miyaura cross-coupling reaction investigated in this study

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“…Pd NP biosynthesis by Hibiscus sabdariffa L. flower extract 0.2 85 Hekmati et al ( 2017 ) 4 Dendritic structure 0.47 90 Sheikh et al ( 2022 ) 5 No support. Pd NP biosynthesis by yerba mate aqueous extract 0.5 91 Schmitt et al ( 2021 ) 6 Corn stem biochar 0.5 78 This work 7 Chitosan/cellulose film 0.5 96 This work 8 Soil-derived humic acid-coated iron-oxide NPs 0.65 90 Chinchole et al ( 2019 ) 9 Cellulose acetate thin film 1.0 90 Faria et al ( 2014 ) …”

“…Efforts have been reported in order to reduce the amount of catalytically active species in reactions (Roy and Uozumi 2018 ) or replace it with a more eco-friendly and less expensive metal (Ma et al 2021 ); reduce the use of auxiliary ligands (Serrano et al 2022 ); employ less toxic solvents (Su et al 2022 ) and bases (Long et al 2019 ); and make the reaction conditions milder through the use of lower temperatures (close to room temperature) (Ma et al 2022 ), microwave heating (Salih 2022 ), sonication (Wilson et al 2018 ), or elimination of the inert atmosphere (Tian et al 2022 ). In addition, the search for new, greener catalytic systems employing biomass sources appears frequently in literature, such as in the use of biomass extracts to prepare metal nanoparticles (NPs) via biogenic routes (Schmitt et al 2021 ) or green solvents applied in carbon–carbon and carbon–heteroatom couplings (Peixoto et al 2022 ). On the other hand, biomass material is also used as a catalytic support of active metals, giving rise to efficient catalysts which employ, for example, biochar (Gholinejad et al 2019 ), calcined materials (Rosa et al 2019 ), or polymeric films (Faria et al 2014 ) in cross-coupling reactions.…”