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Mechanistic insights into the ruthenium-catalysed diene ring-closing metathesis reaction

Nature Chemistry volume 2, pages 571–576 (2010)Cite this article

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Abstract

Ruthenium-catalysed ring-closing metathesis (RCM) is a powerful technique for the preparation of medium-to-large rings in organic synthesis, but the details of the intimate mechanism are obscure. The dynamic behaviour of an RCM-relevant ruthenacyclobutane complex and its reactivity with ethene were studied using low-temperature NMR spectroscopy to illuminate the mechanism of this widely used reaction. These kinetic and thermodynamic experiments allowed for mapping the energy surface of the key steps in the RCM reaction as mediated by Grubbs-type catalysts for alkene metathesis. The highest barrier along the RCM path is only 65 kJ mol−1, which shows that this catalyst has extremely high inherent activity. Furthermore, this transition state corresponds to that connecting the intermediates in this reaction leading to ring opening of the cyclopentene product. This shows that ring closing is kinetically slightly favoured over ring opening, in addition to being driven by the loss of ethene.

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Figure 1: Ring-closing metathesis catalysis.
Figure 2: Degenerate intramolecular exchange processes.
Figure 3: Intermolecular exchange processes.
Figure 4: Reaction of 2 with ethene.
Figure 5: Competitive trapping of a ruthenium methylidene intermediate.
Figure 6: Energetic landscape of diene ring-closing metathesis at 220 K.

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Acknowledgements

Funding for this work was provided by the Natural Sciences and Engineering Research Council of Canada in the form of a Discovery Grant to W.E.P. E.F.v.d.E. thanks the Alberta Ingenuity Fund for financial support in the form of a Studentship. Materia Inc. (Pasadena) is acknowledged for donation of the Grubbs second-generation catalyst I. The authors thank M. Gagné for useful discussions.

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Authors and Affiliations

  1. Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, T2N 1N4, Alberta, Canada

    Edwin F. van der Eide & Warren E. Piers

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  1. Edwin F. van der Eide
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  2. Warren E. Piers
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Contributions

E.F.v.d.E. and W.E.P. conceived and designed the experiments, E.F.v.d.E. carried out the experiments and E.F.v.d.E. and W.E.P. co-wrote the paper.

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Correspondence to Warren E. Piers.

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van der Eide, E., Piers, W. Mechanistic insights into the ruthenium-catalysed diene ring-closing metathesis reaction. Nature Chem 2, 571–576 (2010). https://doi.org/10.1038/nchem.653

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