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End date: 2022 × DDC: 500 × Has files: Yes × Type: Text × Version: publishedVersion × Subject: molecular analysis × WGL Institute: LIKAT ×

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Now showing 1 - 3 of 3
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    Homogeneous 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.
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    Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen
    ([London] : Nature Publishing Group UK, 2020) Cabrero-Antonino, Jose R.; Adam, Rosa; Papa, Veronica; Beller, Matthias
    Catalytic hydrogenation of amides is of great interest for chemists working in organic synthesis, as the resulting amines are widely featured in natural products, drugs, agrochemicals, dyes, etc. Compared to traditional reduction of amides using (over)stoichiometric reductants, the direct hydrogenation of amides using molecular hydrogen represents a greener approach. Furthermore, amide hydrogenation is a highly versatile transformation, since not only higher amines (obtained by C–O cleavage), but also lower amines and alcohols, or amino alcohols (obtained by C–N cleavage) can be selectively accessed by fine tuning of reaction conditions. This review describes the most recent advances in the area of amide hydrogenation using H2 exclusively and molecularly defined homogeneous as well as nano-structured heterogeneous catalysts, with a special focus on catalyst development and synthetic applications.
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    The role of allyl ammonium salts in palladium-catalyzed cascade reactions towards the synthesis of spiro-fused heterocycles
    ([London] : Nature Publishing Group UK, 2020) Ye, Fei; Ge, Yao; Spannenberg, Anke; Neumann, Helfried; Beller, Matthias
    There is a continuous need for designing new and improved synthetic methods aiming at minimizing reaction steps while increasing molecular complexity. In this respect, catalytic, one-pot cascade methodologies constitute an ideal tool for the construction of complex molecules with high chemo-, regio-, and stereoselectivity. Herein, we describe two general and efficient cascade procedures for the synthesis of spiro-fused heterocylces. This transformation combines selective nucleophilic substitution (SN2′), palladium-catalyzed Heck and C–H activation reactions in a cascade manner. The use of allylic ammonium salts and specific Pd catalysts are key to the success of the transformations. The synthetic utility of these methodologies is showcased by the preparation of 48 spiro-fused dihydrobenzofuranes and indolines including a variety of fluorinated derivatives.