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- ItemHomogeneous cobalt-catalyzed reductive amination for synthesis of functionalized primary amines([London] : Nature Publishing Group UK, 2019) Murugesan, Kathiravan; Wei, Zhihong; Chandrashekhar, Vishwas G.; Neumann, Helfried; Spannenberg, Anke; Jiao, Haijun; Beller, Matthias; Jagadeesh, Rajenahally V.The development of earth abundant 3d metal-based catalysts continues to be an important goal of chemical research. In particular, the design of base metal complexes for reductive amination to produce primary amines remains as challenging. Here, we report the combination of cobalt and linear-triphos (bis(2-diphenylphosphinoethyl)phenylphosphine) as the molecularly-defined non-noble metal catalyst for the synthesis of linear and branched benzylic, heterocyclic and aliphatic primary amines from carbonyl compounds, gaseous ammonia and hydrogen in good to excellent yields. Noteworthy, this cobalt catalyst exhibits high selectivity and as a result the -NH2 moiety is introduced in functionalized and structurally diverse molecules. An inner-sphere mechanism on the basis of the mono-cationic [triphos-CoH]+ complex as active catalyst is proposed and supported with density functional theory computation on the doublet state potential free energy surface and H2 metathesis is found as the rate-determining step.
- ItemSimple ruthenium-catalyzed reductive amination enables the synthesis of a broad range of primary amines([London] : Nature Publishing Group UK, 2018) Senthamarai, Thirusangumurugan; Murugesan, Kathiravan; Schneidewind, Jacob; Kalevaru, Narayana V.; Baumann, Wolfgang; Neumann, Helfried; Kamer, Paul C. J.; Beller, Matthias; Jagadeesh, Rajenahally V.The production of primary benzylic and aliphatic amines, which represent essential feedstocks and key intermediates for valuable chemicals, life science molecules and materials, is of central importance. Here, we report the synthesis of this class of amines starting from carbonyl compounds and ammonia by Ru-catalyzed reductive amination using H2. Key to success for this synthesis is the use of a simple RuCl2(PPh3)3 catalyst that empowers the synthesis of >90 various linear and branched benzylic, heterocyclic, and aliphatic amines under industrially viable and scalable conditions. Applying this catalyst, −NH2 moiety has been introduced in functionalized and structurally diverse compounds, steroid derivatives and pharmaceuticals. Noteworthy, the synthetic utility of this Ru-catalyzed amination protocol has been demonstrated by upscaling the reactions up to 10 gram-scale syntheses. Furthermore, in situ NMR studies were performed for the identification of active catalytic species. Based on these studies a mechanism for Ru-catalyzed reductive amination is proposed.
- ItemIdentifying causal gateways and mediators in complex spatio-temporal systems(London : Nature Publishing Group, 2015) Runge, J.; Petoukhov, V.; Donges, J.F.; Hlinka, J.; Jajcay, N.; Vejmelka, M.; Hartman, D.; Marwan, N.; Paluš, M.; Kurths, J.
- ItemReduction of Activated Alkenes by PIII/PV Redox Cycling Catalysis(Weinheim : Wiley-VCH, 2019) Longwitz, Lars; Werner, ThomasThe carbon–carbon double bond of unsaturated carbonyl compounds was readily reduced by using a phosphetane oxide catalyst in the presence of a simple organosilane as the terminal reductant and water as the hydrogen source. Quantitative hydrogenation was observed when 1.0 mol % of a methyl-substituted phosphetane oxide was employed as the catalyst. The procedure is highly selective towards activated double bonds, tolerating a variety of functional groups that are usually prone to reduction. In total, 25 alkenes and two alkynes were hydrogenated to the corresponding alkanes in excellent yields of up to 99 %. Notably, less active poly(methylhydrosiloxane) could also be utilized as the terminal reductant. Mechanistic investigations revealed the phosphane as the catalyst resting state and a protonation/deprotonation sequence as the crucial step in the catalytic cycle. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemDevelopment of a control system for the teat-end vacuum in individual quarter milking systems(Basel : MDPI, 2013) Ströbel, Ulrich; Rose-Meierhöfer, Sandra; Öz, Hülya; Brunsch, ReinerProgress in sensor technique and electronics has led to a decrease in the costs of electronic and sensor components. In modern dairy farms, having udders in good condition, a lower frequency of udder disease and an extended service life of dairy cows will help ensure competitiveness. The objective of this study was to develop a teat-end vacuum control system with individual quarter actor reaction. Based on a review of the literature, this system is assumed to protect the teat tissue. It reduces the mean teat-end vacuum in the maximum vacuum phase (b) to a level of 20 kPa at a flow rate of 0.25 L/min per quarter. At flow rates higher than 1.50 L/min per quarter, the teat-end vacuum can be controlled to a level of 30 kPa, because in this case it is desirable to have a higher vacuum for the transportation of the milk to the receiver. With this system it is possible for the first time to supply the teat end with low vacuum at low flow rates and with higher vacuum at increasing flow rates in a continuous process with a three second reaction-rate on individual quarter level. This system is completely automated.