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A General and Highly Selective Palladium-Catalyzed Hydroamidation of 1,3-Diynes
2021, Liu, Jiawang, Schneider, Carolin, Yang, Ji, Wei, Zhihong, Jiao, Haijun, Franke, Robert, Jackstell, Ralf, Beller, Matthias
A chemo-, regio-, and stereoselective mono-hydroamidation of (un)symmetrical 1,3-diynes is described. Key for the success of this novel transformation is the utilization of an advanced palladium catalyst system with the specific ligand Neolephos. The synthetic value of this general approach to synthetically useful α-alkynyl-α, β-unsaturated amides is showcased by diversification of several structurally complex molecules and marketed drugs. Control experiments and density-functional theory (M06L-SMD) computations also suggest the crucial role of the substrate in controlling the regioselectivity of unsymmetrical 1,3-diynes. © 2020 The Authors. Published by Wiley-VCH GmbH
Cobalt-Catalyzed Aqueous Dehydrogenation of Formic Acid
2019, Zhou, Wei, Wei, Zhihong, Spannenberg, Anke, Jiao, Haijun, Junge, Kathrin, Junge, Henrik, Beller, Matthias
Among the known liquid organic hydrogen carriers, formic acid attracts increasing interest in the context of safe and reversible storage of hydrogen. Here, the first molecularly defined cobalt pincer complex is disclosed for the dehydrogenation of formic acid in aqueous medium under mild conditions. Crucial for catalytic activity is the use of the specific complex 3. Compared to related ruthenium and manganese complexes 7 and 8, this optimal cobalt complex showed improved performance. DFT computations support an innocent non-classical bifunctional outer-sphere mechanism on the triplet state potential energy surface. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol-Functionalized Phosphonium Salts
2021, Hu, Yuya, Wei, Zhihong, Frey, Anna, Kubis, Christoph, Ren, Chang-Yue, Spannenberg, Anke, Jiao, Haijun, Werner, Thomas
A series of hydroxy-functionalized phosphonium salts were studied as bifunctional catalysts for the conversion of CO2 with epoxides under mild and solvent-free conditions. The reaction in the presence of a phenol-based phosphonium iodide proceeded via a first order rection kinetic with respect to the substrate. Notably, in contrast to the aliphatic analogue, the phenol-based catalyst showed no product inhibition. The temperature dependence of the reaction rate was investigated, and the activation energy for the model reaction was determined from an Arrhenius-plot (Ea =39.6 kJ mol-1 ). The substrate scope was also evaluated. Under the optimized reaction conditions, 20 terminal epoxides were converted at room temperature to the corresponding cyclic carbonates, which were isolated in yields up to 99 %. The reaction is easily scalable and was performed on a scale up to 50 g substrate. Moreover, this method was applied in the synthesis of the antitussive agent dropropizine starting from epichlorohydrin and phenylpiperazine. Furthermore, DFT calculations were performed to rationalize the mechanism and the high efficiency of the phenol-based phosphonium iodide catalyst. The calculation confirmed the activation of the epoxide via hydrogen bonding for the iodide salt, which facilitates the ring-opening step. Notably, the effective Gibbs energy barrier regarding this step is 97 kJ mol-1 for the bromide and 72 kJ mol-1 for the iodide salt, which explains the difference in activity.
A Stable Manganese Pincer Catalyst for the Selective Dehydrogenation of Methanol
2016-12-2, Andérez-Fernández, María, Vogt, Lydia K., Fischer, Steffen, Zhou, Wei, Jiao, Haijun, Garbe, Marcel, Elangovan, Saravanakumar, Junge, Kathrin, Junge, Henrik, Ludwig, Ralf, Beller, Matthias
For the first time, structurally defined manganese pincer complexes catalyze the dehydrogenation of aqueous methanol to hydrogen and carbon dioxide, which is a transformation of interest with regard to the implementation of a hydrogen and methanol economy. Excellent long-term stability was demonstrated for the Mn-PNPiPr catalyst, as a turnover of more than 20 000 was reached. In addition to methanol, other important hydrogen carriers were also successfully dehydrogenated.
Zirconium-Catalyzed Atom-Economical Synthesis of 1,1-Diborylalkanes from Terminal and Internal Alkenes
2020, Wang, Xianjin, Cui, Xin, Li, Sida, Wang, Yue, Xia, Chungu, Jiao, Haijun, Wu, Lipeng
A general and atom-economical synthesis of 1,1-diborylalkanes from alkenes and a borane without the need for an additional H2 acceptor is reported for the first time. The key to our success is the use of an earth-abundant zirconium-based catalyst, which allows a balance of self-contradictory reactivities (dehydrogenative boration and hydroboration) to be achieved. Our method avoids using an excess amount of another alkene as an H2 acceptor, which was required in other reported systems. Furthermore, substrates such as simple long-chain aliphatic alkenes that did not react before also underwent 1,1-diboration in our system. Significantly, the unprecedented 1,1-diboration of internal alkenes enabled the preparation of 1,1-diborylalkanes. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
Ligand-Controlled Palladium-Catalyzed Carbonylation of Alkynols : Highly Selective Synthesis of α-Methylene-β-Lactones
2020, Ge, Yao, Ye, Fei, Liu, Jiawang, Yang, Ji, Spannenberg, Anke, Jiao, Haijun, Jackstell, Ralf, Beller, Matthias
The first general and regioselective Pd-catalyzed cyclocarbonylation to give α-methylene-β-lactones is reported. Key to the success for this process is the use of a specific sterically demanding phosphine ligand based on N-arylated imidazole (L11) in the presence of Pd(MeCN)2Cl2 as pre-catalyst. A variety of easily available alkynols provide under additive-free conditions the corresponding α-methylene-β-lactones in moderate to good yields with excellent regio- and diastereoselectivity. The applicability of this novel methodology is showcased by the direct carbonylation of biologically active molecules including natural products. © 2020 The Authors. Published by Wiley-VCH GmbH
Palladium-Catalyzed Cascade Carbonylation to α,β-Unsaturated Piperidones via Selective Cleavage of Carbon-Carbon Triple Bonds
2021, Ge, Yao, Ye, Fei, Yang, Ji, Spannenberg, Anke, Jiao, Haijun, Jackstell, Ralf, Beller, Matthias
A direct and selective synthesis of α,β-unsaturated piperidones by a new palladium-catalyzed cascade carbonylation is described. In the presented protocol, easily available propargylic alcohols react with aliphatic amines to provide a broad variety of interesting heterocycles. Key to the success of this transformation is a remarkable catalytic cleavage of the present carbon–carbon triple bond by using a specific catalyst with 2-diphenylphosphinopyridine as ligand and appropriate reaction conditions. Mechanistic studies and control experiments revealed branched unsaturated acid 11 as crucial intermediate. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH