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Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran

Nature Chemistry volume 2, pages 588–591 (2010)Cite this article

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Abstract

The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium–zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC4) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium–magnesium or sodium–manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C4 fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates.

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Figure 1: Known outcomes of THF metallation reactions.
Figure 2: Bond breakages and formal anionic products of the new reactions from the perspective of THF.
Figure 3: Syntheses of inverse crown ethers 3 and 4 and 1,4-bimetallated butadienes 5 and 6.
Figure 4: Molecular structure of 5.
Figure 5: Molecular structure of 4.

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Acknowledgements

This work was supported by the UK Engineering and Physical Science Research Council. R.E.M. thanks the Royal Society/Wolfson Foundation for a research merit award. J.K. thanks the Royal Society of Edinburgh/BP Trust for a research Fellowship. We also thank J.A. Parkinson for advice on the NMR spectroscopic experiments.

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Authors and Affiliations

  1. Department of Pure and Applied Chemistry, WestCHEM, University of Strathclyde, Glasgow, G1 1XL, UK

    Robert E. Mulvey, Victoria L. Blair, Alan R. Kennedy & Jan Klett

  2. School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK

    William Clegg & Luca Russo

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  1. Robert E. Mulvey
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  2. Victoria L. Blair
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  4. Alan R. Kennedy
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Contributions

R.E.M. conceived the project and wrote the manuscript. J.K. added ideas and designed and performed some experiments. V.L.B. performed most syntheses and spectroscopic studies. W.C., A.R.K. and L.R. carried out X-ray crystallographic work.

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Correspondence to Robert E. Mulvey.

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The authors declare no competing financial interests.

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Crystallographic information for compound 4 (CIF 13 kb)

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Crystallographic information for compound 5 (CIF 29 kb)

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Crystallographic information for compound 6 (CIF 34 kb)

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Mulvey, R., Blair, V., Clegg, W. et al. Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran. Nature Chem 2, 588–591 (2010). https://doi.org/10.1038/nchem.667

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