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Superelectrophilic aluminium(iii)–ion pairs promote a distinct reaction path for carbonyl–olefin ring-closing metathesis

Nature Catalysis volume 3, pages 787–796 (2020)Cite this article

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Abstract

Catalytic carbonyl–olefin metathesis reactions represent powerful synthetic strategies for alkene formation. Successful approaches for carbonyl–olefin ring-closing, ring-opening and cross metathesis have been developed in recent years, but current limitations hamper the generality of these transformations. Stronger, more efficient catalytic systems are needed to further broaden the scope of these transformations while they prevent undesired reaction pathways. Here we report the development of an aluminium-based heterobimetallic ion pair as a superior catalyst that promotes carbonyl–olefin ring-closing metathesis via a distinct reaction mechanism and allows access to six- and seven-membered rings, which suffer from low yields and poor conversion under previously reported conditions. Mechanistic investigations support a distinct reaction profile in which two productive reaction pathways competitively form metathesis products. These insights are expected to have important implications in the catalyst design and development for carbonyl–olefin metathesis and enable future advances to ultimately expand the synthetic utility of these transformations.

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Fig. 1: Scaffolds accessible via catalytic carbonyl–olefin metathesis.
Fig. 2: Superelectrophilic ion pairs are strong Lewis acids for the carbonyl–olefin metathesis of six-membered rings.
Fig. 3: Reaction scope of Al(iii)–ion pairs as superelectrophilic catalysts for metathesis.
Fig. 4: Comparison of rates of product formation.
Fig. 5: Carbonyl–ene product forms reversibly.
Fig. 6: Two potential pathways for carbonyl–olefin metathesis of medium-sized rings.
Fig. 7: Kinetic isotope studies.
Fig. 8: Mechanistic hypothesis.

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Data availability

Experimental data as well as 1H and 13C NMR spectra for all the new compounds prepared in the course of these studies are provided in the Supplementary Information. Additional information available as part of the Supplementary Information files include synthetic procedures and details relevant to the reaction optimization. 1H NMR spectroscopy files used for kinetic experiments and other raw data that support the findings of this paper are available from the corresponding author upon reasonable request.

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Acknowledgements

We thank the NIH/National Institute of General Medical Sciences (R01-GM118644), the Alfred P. Sloan Foundation, the David and Lucile Packard Foundation and the Camille and Henry Dreyfus Foundation for financial support. R.B.W. thanks the National Science Foundation for a predoctoral fellowship. J.L.G.-L. thanks CONACyT for a postdoctoral fellowship. We thank J. P. Reid for helpful guidance with the conformational searches associated with the computational studies. We are thankful to R. Wiscons for X-ray powder diffraction studies. We are grateful to P. Zimmerman for helpful discussions regarding the computational studies. We thank J. Kiernicki for helpful guidance with the experimental design to support the active catalyst.

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  1. These authors contributed equally: A. J. Davis and R. B. Watson.

Authors and Affiliations

  1. Willard Henry Dow Laboratory, Department of Chemistry, University of Michigan, Ann Arbor, MI, USA

    Ashlee J. Davis, Rebecca B. Watson, Daniel J. Nasrallah, Jessica L. Gomez-Lopez & Corinna S. Schindler

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Contributions

A.J.D., R.B.W. and C.S.S. conceived the project and synthesized all the substrates and corresponding intermediates. J.L.G.-L. performed the reaction optimization experiments, prepared susbtrates for title reactions, and aided in performing kinetic studies. A.J.D. performed all the title reactions and experimental studies. D.J.N. performed all the computational studies. All the authors discussed the results and contributed to the manuscript preparation.

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Correspondence to Corinna S. Schindler.

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Supplementary Figs. 1–7, Tables 1–4, discussion, methods and references.

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Davis, A.J., Watson, R.B., Nasrallah, D.J. et al. Superelectrophilic aluminium(iii)–ion pairs promote a distinct reaction path for carbonyl–olefin ring-closing metathesis. Nat Catal 3, 787–796 (2020). https://doi.org/10.1038/s41929-020-00499-5

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