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    A General Regioselective Synthesis of Alcohols by Cobalt-Catalyzed Hydrogenation of Epoxides
    (Weinheim : Wiley-VCH, 2020) Liu, Weiping; Leischner, Thomas; Li, Wu; Junge, Kathrin; Beller, Matthias
    A straightforward methodology for the synthesis of anti-Markovnikov-type alcohols is presented. By using a specific cobalt triphos complex in the presence of Zn(OTf)2 as an additive, the hydrogenation of epoxides proceeds with high yields and selectivities. The described protocol shows a broad substrate scope, including multi-substituted internal and terminal epoxides, as well as a good functional-group tolerance. Various natural-product derivatives, including steroids, terpenoids, and sesquiterpenoids, gave access to the corresponding alcohols in moderate-to-excellent yields. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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    Cascade Synthesis of Pyrroles from Nitroarenes with Benign Reductants Using a Heterogeneous Cobalt Catalyst
    (Weinheim : Wiley-VCH, 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
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    Synthesis of Molybdenum Pincer Complexes and Their Application in the Catalytic Hydrogenation of Nitriles
    (Weinheim : Wiley-VCH Verlag, 2020) Leischner, Thomas; Spannenberg, Anke; Junge, Kathrin; Beller, Matthias
    A series of molybdenum(0), (I) and (II) complexes ligated by different PNP and NNN pincer ligands were synthesized and structurally characterized. Along with previously described Mo−PNP complexes Mo-1 and Mo-2, all prepared compounds were tested in the catalytic hydrogenation of aromatic nitriles to primary amines. Among the applied catalysts, Mo-1 is particularly well suited for the hydrogenation of electron-rich benzonitriles. Additionally, two aliphatic nitriles were transformed into the desired products in 80 and 86 %, respectively. Moreover, catalytic intermediate Mo-1a was isolated and its role in the catalytic cycle was subsequently demonstrated. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.