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      N-formyl-stabilizing quasi-catalytic species afford rapid and selective solvent-free amination of biomass-derived feedstocks

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          Abstract

          Nitrogen-containing compounds, especially primary amines, are vital building blocks in nature and industry. Herein, a protocol is developed that shows in situ formed N-formyl quasi-catalytic species afford highly selective synthesis of formamides or amines with controllable levels from a variety of aldehyde- and ketone-derived platform chemical substrates under solvent-free conditions. Up to 99% yields of mono-substituted formamides are obtained in 3 min. The C-N bond formation and N-formyl species are prevalent in the cascade reaction sequence. Kinetic and isotope labeling experiments explicitly demonstrate that the C-N bond is activated for subsequent hydrogenation, in which formic acid acts as acid catalyst, hydrogen donor and as N-formyl species source that stabilize amine intermediates elucidated with density functional theory. The protocol provides access to imides from aldehydes, ketones, carboxylic acids, and mixed-substrates, requires no special catalysts, solvents or techniques and provides new avenues for amination chemistry.

          Abstract

          Processes for efficient production of primary, secondary or ternary aminated compounds are constant challenges for chemical and pharmaceutical industries. Here, the authors develop selective and sustainable amination chemistry widely applicable to chemical substrates via formic acid.

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          Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides

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            Efficient dehydrogenation of formic acid using an iron catalyst.

            Hydrogen is one of the essential reactants in the chemical industry, though its generation from renewable sources and storage in a safe and reversible manner remain challenging. Formic acid (HCO(2)H or FA) is a promising source and storage material in this respect. Here, we present a highly active iron catalyst system for the liberation of H(2) from FA. Applying 0.005 mole percent of Fe(BF(4))(2)·6H(2)O and tris[(2-diphenylphosphino)ethyl]phosphine [P(CH(2)CH(2)PPh(2))(3), PP(3)] to a solution of FA in environmentally benign propylene carbonate, with no further additives or base, affords turnover frequencies up to 9425 per hour and a turnover number of more than 92,000 at 80°C. We used in situ nuclear magnetic resonance spectroscopy, kinetic studies, and density functional theory calculations to explain possible reaction mechanisms.
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              Ab initio study of ionic solutions by a polarizable continuum dielectric model

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                Author and article information

                Contributors
                zhenfang@njau.edu.cn
                meijin@scf.che.tohoku.ac.jp
                smith@scf.che.tohoku.ac.jp
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                11 February 2019
                11 February 2019
                2019
                : 10
                Affiliations
                [1 ]ISNI 0000 0000 9750 7019, GRID grid.27871.3b, Biomass Group, College of Engineering, , Nanjing Agricultural University, ; 40 Dianjiangtai Road, 210031 Nanjing, Jiangsu China
                [2 ]ISNI 0000 0001 2248 6943, GRID grid.69566.3a, Graduate School of Environmental Studies, , Tohoku University, ; 6-6-11, Aoba, Aramaki, Aoba-ku, Sendai, 980-8579 Japan
                [3 ]ISNI 0000 0001 2248 6943, GRID grid.69566.3a, Research Center of Supercritical Fluid Technology, Graduate School of Engineering, , Tohoku University, ; 6-6-11, Aoba, Aramaki, Aoba-ku, Sendai, 980-8579 Japan
                [4 ]ISNI 0000 0004 0398 8763, GRID grid.6852.9, Department of Chemical Engineering and Chemistry, Laboratory of Inorganic Materials Chemistry, Schuit Institute of Catalysis, , Eindhoven University of Technology, ; P.O. Box 513, 5600 MB Eindhoven, The Netherlands
                Article
                8577
                10.1038/s41467-019-08577-4
                6370847
                30741927
                © The Author(s) 2019

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

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