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A frustrated-Lewis-pair approach to catalytic reduction of alkynes to cis-alkenes

Nature Chemistry volume 5, pages 718–723 (2013)Cite this article

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Abstract

Frustrated Lewis pairs are compounds containing both Lewis acidic and Lewis basic moieties, where the formation of an adduct is prevented by steric hindrance. They are therefore highly reactive, and have been shown to be capable of heterolysis of molecular hydrogen, a property that has led to their use in hydrogenation reactions of polarized multiple bonds. Here, we describe a general approach to the hydrogenation of alkynes to cis-alkenes under mild conditions using the unique ansa-aminohydroborane as a catalyst. Our approach combines several reactions as the elementary steps of the catalytic cycle: hydroboration (substrate binding), heterolytic hydrogen splitting (typical frustrated-Lewis-pair reactivity) and facile intramolecular protodeborylation (product release). The mechanism is verified by experimental and computational studies.

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Figure 1: FLP-catalysed hydrogenation of multiple C–C bonds.
Figure 2: Mechanism of catalytic hydrogenation of alkynes into cis-alkenes.
Figure 3: Solution-phase Gibbs free energy diagram computed for the hydrogenation of but-2-yne (10a).
Figure 4: Reaction of 6 and 8 with alkenes.
Figure 5: Reaction of aminoborane 6 with hex-1-yne and H2.

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Acknowledgements

The authors acknowledge financial support from the Academy of Finland (139550) and the Hungarian Research Foundation (OTKA, grant K-81927) and COST action CM0905 (Organocatalysis). The authors also thank A. Reznichenko for discussions and corrections during the preparation of the manuscript, M. Lindqvist for corrections and S. Heikkinen for help with NMR measurements.

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Authors and Affiliations

  1. Department of Chemistry, Laboratory of Inorganic Chemistry, University of Helsinki, PO Box 55, FIN-00014, Finland

    Konstantin Chernichenko, Martin Nieger, Markku Leskelä & Timo Repo

  2. Institute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, PO Box 17, H-1525, Budapest, Hungary

    Ádám Madarász & Imre Pápai

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  1. Konstantin Chernichenko
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Contributions

K.C. and T.R. conceived and K.C. carried out the experiments. A.M. and I.P. designed and performed the DFT studies. All authors discussed and co-wrote the paper.

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Correspondence to Imre Pápai or Timo Repo.

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Chernichenko, K., Madarász, Á., Pápai, I. et al. A frustrated-Lewis-pair approach to catalytic reduction of alkynes to cis-alkenes. Nature Chem 5, 718–723 (2013). https://doi.org/10.1038/nchem.1693

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