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Zeolites as equilibrium-shifting agents in shuttle catalysis

Nature Catalysis volume 6, pages 495–505 (2023)Cite this article

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Abstract

The catalytic shuttling of functional moieties has emerged as a promising strategy to substitute and diversify traditional hydrofunctionalization technologies. However, these reactions are reversible due to their isodesmic nature, which limits their applicability to a select array of donor and acceptor molecules, and poses substantial challenges with regard to atom economy and practicality. Here we show an approach that harnesses the shape-selective and catalytic properties of zeolites to drive the shuttling equilibrium of transfer hydrocyanation and transfer hydroformylation reactions to near-completion. The zeolites irreversibly convert the transfer reaction co-products in an exergonic tandem reaction while excluding the substrates via pore size restrictions. Through fine-tuning of the zeolite’s properties, yield increases of up to 80% can be achieved, enabling diversification of nitrile donors to propionitrile and aldehyde acceptors to unactivated olefins. Mechanistic and spectroscopic studies highlight the unique synergy between the zeolites and the homogeneous transfer catalysts.

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Fig. 1: Driving the equilibrium of catalytic shuttle reactions.
Fig. 2: Effect of zeolites on reaction performance.
Fig. 3: Tandem reactions catalysed by zeolites containing acid and/or transition metal sites.
Fig. 4: Mechanistic and spectroscopic studies of H-ZSM-5-assisted transfer hydrocyanation with propionitrile.
Fig. 5: Substrate scope of the zeolite-assisted transfer hydrocyanation.
Fig. 6: Substrate scope of the zeolite-assisted transfer hydroformylation.

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The findings of this study are available within the article and its supplementary information. All data are available from the authors upon reasonable request.

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Acknowledgements

We thank J. Vercammen for insights on zeolite synthesis and manipulation, K. Lomachenko for help with XAS measurements, G. O’Rourke for assistance with TGA experiments, C. Marquez for help with ICP measurements, and C. Cheung for providing the scanning electron microscopy images. The XAS experiments were performed at beamline BM23 of the European Synchrotron Radiation Facility (ESRF, Grenoble, France). D.D.V. and J.D. are grateful to KULeuven (C1 project) and FWO (G0781118N with ARSS, Slovenia; G0F2320N) for funding. A.K. and G.M. acknowledge financial support from the Slovenian Research Agency (research core funding no. P1-0021 and project no. N1-0079).

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Authors and Affiliations

  1. Centre for Membrane Separations, Adsorption, Catalysis, and Spectroscopy for Sustainable Solutions (cMACS), KU Leuven, Leuven, Belgium

    Jesse Dallenes, Jonas Wuyts, Niels Van Velthoven & Dirk De Vos

  2. Department of Inorganic Chemistry and Technology, National Institute of Chemistry, Ljubljana, Slovenia

    Andraž Krajnc & Gregor Mali

  3. The Smart Materials Research Institute, Southern Federal University, Rostov-on-Don, Russia

    Oleg A. Usoltsev

  4. Paul Scherrer Institute, Villigen, Switzerland

    Aram L. Bugaev

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Contributions

D.D.V. and J.D. were responsible for the conception, design and interpretation of the experiments. J.D. and J.W. performed the experiments and analysed the data. J.D., N.V.V. and A.L.B. conceived the design of the XAS experiments, and A.L.B. and O.A.U. were responsible for data processing. A.K. and G.M. conceived and performed the NMR experiments. The paper was written by J.D. and D.D.V., with contributions from all authors.

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Correspondence to Dirk De Vos.

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Supplementary Methods, Discussion, Figs. 1–47, Tables 1–28 and References.

Supplementary Data 1

Computational geometry optimization data.

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Dallenes, J., Wuyts, J., Van Velthoven, N. et al. Zeolites as equilibrium-shifting agents in shuttle catalysis. Nat Catal 6, 495–505 (2023). https://doi.org/10.1038/s41929-023-00967-8

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