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Proof of a Reversible, Pairwise Hydrogen Transfer during the Homogeneously Rhodium(I)-Catalyzed Hydrogenation of α,β-Unsaturated Carbonic Acid Derivatives with In Situ NMR Spectroscopy and Parahydrogen

Authors

  • Dipl.-Chem. Andreas Harthun,

    1. Institut für Theoretische und Physikalische Chemie der Universität, Wegelerstrasse 12, D-53115 Bonn (Germany), Fax: Int. code +(228)-732551, e-mail: bargon@rs1.thch.uni-bonn.de
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  • Prof. Dr. Rüdiger Selke,

    Corresponding author
    1. Max-Planck-Gesellschaft, Arbeitsgruppe “Asymmetrische Katalyse” an der Universität Rostock, Buchbinderstrasse 5-6, D-18055 Rostock (Germany), Fax: Int. code +(381)46693-24
    • Max-Planck-Gesellschaft, Arbeitsgruppe “Asymmetrische Katalyse” an der Universität Rostock, Buchbinderstrasse 5-6, D-18055 Rostock (Germany), Fax: Int. code +(381)46693-24
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  • Prof. Dr. Joachim Bargon

    Corresponding author
    1. Institut für Theoretische und Physikalische Chemie der Universität, Wegelerstrasse 12, D-53115 Bonn (Germany), Fax: Int. code +(228)-732551, e-mail: bargon@rs1.thch.uni-bonn.de
    • Institut für Theoretische und Physikalische Chemie der Universität, Wegelerstrasse 12, D-53115 Bonn (Germany), Fax: Int. code +(228)-732551, e-mail: bargon@rs1.thch.uni-bonn.de
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  • This work was financially supported by the Volkswagenstiftung, the Bundesministerium für Bildung, Wissenschaft, Forschung und Technologie (BMFT), the Deutsche Forschungsgemeinschaft (SFB 334: Wechselwirkungen in Molekülen), and the Fonds der Chemischen Industrie.

Abstract

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Pairwise exchange of geminal protons in unsaturated carbonic acid derivatives of the type H2C[DOUBLE BOND]C(R)COOR′ during the rhodium(I)-catalyzed hydrogenation [Eq. (a)] has been proven conclusively for the first time by using in situ NMR spectroscopy and parahydrogen (PHIP method). The most important conclusion is that the formation of the hydridoalkyl intermediates must be a reversible reaction.

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