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Iron(III)-catalysed carbonyl–olefin metathesis

Abstract

The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon–carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries1. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism2. While the corresponding carbonyl–olefin metathesis reaction can also be used to construct carbon–carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl–olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl–olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

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Figure 1: Olefination and metathesis reactions for the formation of alkenes.
Figure 2: Initial evaluation of the catalytic carbonyl–olefin metathesis reaction.
Figure 3: Scope of the iron(III)-catalysed carbonyl–olefin metathesis reaction.
Figure 4: Alkene evaluation in the catalytic carbonyl–olefin metathesis reaction.
Figure 5: Mechanistic hypothesis for the iron(III)-chloride-catalysed carbonyl–olefin metathesis reaction.

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Acknowledgements

This work was supported by the Petroleum Research Fund (PRF#54688-DNI1) and start-up funds provided by the University of Michigan. J.R.L. thanks the National Science Foundation for a predoctoral fellowship. P.M.Z. thanks the Office of Naval Research for support under grant N00014-14-1-0551 and the Petroleum Research Fund (PRF#54267-DNI6). We are grateful to A. Speelman, A. McQuarters and N. Lehnert at the University of Michigan for helpful discussions.

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J.R.L., J.B.G. and C.S.S. devised the experiments, prepared the starting materials and the products. P.M.Z. conducted the theoretical investigations. J.R.L., J.B.G., P.M.Z. and C.S.S. prepared this manuscript for publication.

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Correspondence to Corinna S. Schindler.

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The authors declare no competing financial interests.

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Supplementary Information

This file contains Supplementary Tables 1-8 and 6 Supplementary Figures. Also included are Supplementary Methods and Materials, Supplementary Results, X-Ray crystallographic data and NMR Spectral data, which contains 1H and 13C NMR data for all new compounds. (PDF 34111 kb)

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Ludwig, J., Zimmerman, P., Gianino, J. et al. Iron(III)-catalysed carbonyl–olefin metathesis. Nature 533, 374–379 (2016). https://doi.org/10.1038/nature17432

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