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Cascade Synthesis of Pyrroles from Nitroarenes with Benign Reductants Using a Heterogeneous Cobalt Catalyst
2020, Ryabchuk, Pavel, Leischner, Thomas, Kreyenschulte, Carsten, Spannenberg, Anke, Junge, Kathrin, Beller, Matthias
A bifunctional 3d-metal catalyst for the cascade synthesis of diverse pyrroles from nitroarenes is presented. The optimal catalytic system Co/NGr-C@SiO2-L is obtained by pyrolysis of a cobalt-impregnated composite followed by subsequent selective leaching. In the presence of this material, (transfer) hydrogenation of easily available nitroarenes and subsequent Paal–Knorr/Clauson-Kass condensation provides >40 pyrroles in good to high yields using dihydrogen, formic acid, or a CO/H2O mixture (WGSR conditions) as reductant. In addition to the favorable step economy, this straightforward domino process does not require any solvents or external co-catalysts. The general synthetic utility of this methodology was demonstrated on a variety of functionalized substrates including the preparation of biologically active and pharmaceutically relevant compounds, for example, (+)-Isamoltane. © 2020 The Authors. Published by Wiley-VCH GmbH
A robust iron catalyst for the selective hydrogenation of substituted (iso)quinolones
2018, Sahoo, Basudev, Kreyenschulte, Carsten, Agostini, Giovanni, Lund, Henrik, Bachmann, Stephan, Scalone, Michelangelo, Junge, Kathrin, Beller, Matthias
By applying N-doped carbon modified iron-based catalysts, the controlled hydrogenation of N-heteroarenes, especially (iso)quinolones, is achieved. Crucial for activity is the catalyst preparation by pyrolysis of a carbon-impregnated composite, obtained from iron(ii) acetate and N-aryliminopyridines. As demonstrated by TEM, XRD, XPS and Raman spectroscopy, the synthesized material is composed of Fe(0), Fe3C and FeNx in a N-doped carbon matrix. The decent catalytic activity of this robust and easily recyclable Fe-material allowed for the selective hydrogenation of various (iso)quinoline derivatives, even in the presence of reducible functional groups, such as nitriles, halogens, esters and amides. For a proof-of-concept, this nanostructured catalyst was implemented in the multistep synthesis of natural products and pharmaceutical lead compounds as well as modification of photoluminescent materials. As such this methodology constitutes the first heterogeneous iron-catalyzed hydrogenation of substituted (iso)quinolones with synthetic importance.
A General Catalyst Based on Cobalt Core–Shell Nanoparticles for the Hydrogenation of N-Heteroarenes Including Pyridines
2020, Murugesan, Kathiravan, Chandrashekhar, Vishwas G., Kreyenschulte, Carsten, Beller, Matthias, Jagadeesh, Rajenahally V.
Herein, we report the synthesis of specific silica-supported Co/Co3O4 core–shell based nanoparticles prepared by template synthesis of cobalt-pyromellitic acid on silica and subsequent pyrolysis. The optimal catalyst material allows for general and selective hydrogenation of pyridines, quinolines, and other heteroarenes including acridine, phenanthroline, naphthyridine, quinoxaline, imidazo[1,2-a]pyridine, and indole under comparably mild reaction conditions. In addition, recycling of these Co nanoparticles and their ability for dehydrogenation catalysis are showcased. © 2020 The Authors. Published by Wiley-VCH GmbH
Synthesis of Single Atom Based Heterogeneous Platinum Catalysts: High Selectivity and Activity for Hydrosilylation Reactions
2017, Cui, Xinjiang, Junge, Kathrin, Dai, Xingchao, Kreyenschulte, Carsten, Pohl, Marga-Martina, Wohlrab, Sebastian, Shi, Feng, Brückner, Angelika, Beller, Matthias
Catalytic hydrosilylation represents a straightforward and atom-efficient methodology for the creation of C-Si bonds. In general, the application of homogeneous platinum complexes prevails in industry and academia. Herein, we describe the first heterogeneous single atom catalysts (SACs), which are conveniently prepared by decorating alumina nanorods with platinum atoms. The resulting stable material efficiently catalyzes hydrosilylation of industrially relevant olefins with high TON (≈105). A variety of substrates is selectively hydrosilylated including compounds with sensitive reducible and other functional groups (N, B, F, Cl). The single atom based catalyst shows significantly higher activity compared to related Pt nanoparticles.
Iron/N-doped graphene nano-structured catalysts for general cyclopropanation of olefins
2020, Sarkar, Abhijnan, Formenti, Dario, Ferretti, Francesco, Kreyenschulte, Carsten, Bartling, Stephan, Junge, Kathrin, Beller, Matthias, Ragaini, Fabio
The first examples of heterogeneous Fe-catalysed cyclopropanation reactions are presented. Pyrolysis of in situ-generated iron/phenanthroline complexes in the presence of a carbonaceous material leads to specific supported nanosized iron particles, which are effective catalysts for carbene transfer reactions. Using olefins as substrates, cyclopropanes are obtained in high yields and moderate diastereoselectivities. The developed protocol is scalable and the activity of the recycled catalyst after deactivation can be effectively restored using an oxidative reactivation protocol under mild conditions. This journal is © The Royal Society of Chemistry.
Hydrogenation of terminal and internal olefins using a biowaste-derived heterogeneous cobalt catalyst
2018, Scharnagl, Florian Korbinian, Hertrich, Maximilian Franz, Ferretti, Francesco, Kreyenschulte, Carsten, Lund, Henrik, Jackstell, Ralf, Beller, Matthias
Hydrogenation of olefins is achieved using biowaste-derived cobalt chitosan catalysts. Characterization of the optimal Co@Chitosan-700 by STEM (scanning transmission electron microscopy), EELS (electron energy loss spectroscopy), PXRD (powder x-ray diffraction), and elemental analysis revealed the formation of a distinctive magnetic composite material with high metallic Co content. The general performance of this catalyst is demonstrated in the hydrogenation of 50 olefins including terminal, internal, and functionalized derivatives, as well as renew-ables. Using this nonnoble metal composite, hydrogenation of terminal C==C double bonds occurs under very mild and benign conditions (water or methanol, 40° to 60°C). The utility of Co@Chitosan-700 is showcased for efficient hydrogenation of the industrially relevant examples diisobutene, fatty acids, and their triglycerides. Because of the magnetic behavior of this material and water as solvent, product separation and recycling of the catalyst are straightforward.
Correction: A robust iron catalyst for the selective hydrogenation of substituted (iso)quinolones
2018, Sahoo, Basudev, Kreyenschulte, Carsten, Agostini, Giovanni, Lund, Henrik, Bachmann, Stephan, Scalone, Michelangelo, Junge, Kathrin, Beller, Matthias
The authors regret that the term “(iso)quinolones” was used throughout the article, including the title, when the correct term should be “(iso)quinolines”. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.
Selective cobalt nanoparticles for catalytic transfer hydrogenation of N-heteroarenes
2017, Chen, Feng, Sahoo, Basudev, Kreyenschulte, Carsten, Lund, Henrik, Zeng, Min, He, Lin, Junge, Kathrin, Beller, Matthias
Nitrogen modified cobalt catalysts supported on carbon were prepared by pyrolysis of the mixture generated from cobalt(ii) acetate in aqueous solution of melamine or waste melamine resins, which are widely used as industrial polymers. The obtained nanostructured materials catalyze the transfer hydrogenation of N-heteroarenes with formic acid in the absence of base. The optimal Co/Melamine-2@C-700 catalyst exhibits high activity and selectivity for the dehydrogenation of formic acid into molecular hydrogen and carbon dioxide and allows for the reduction of diverse N-heteroarenes including substrates featuring sensitive functional groups.