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Ring contraction of metallacyclobutadiene to metallacyclopropene driven by π- and σ-aromaticity relay

Nature Synthesis volume 2, pages 67–75 (2023)Cite this article

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Abstract

π-Aromaticity is an important driving force in directing the synthesis of aromatic compounds; in contrast, reactions induced by σ-aromaticity are uncommon. Here we report a strategy based on π- and σ-aromaticity relays to realize the structurally defined ring contraction of metallacyclobutadiene to metallacyclopropene. This reaction involves the release of the π-antiaromaticity of metallacyclobutadiene to afford a π-aromatic intermediate, followed by ring reclosure to generate σ-aromatic metallacyclopropene. The ring opening–reclosing mechanism and versatile switching of the aromaticity of the metallacyclic species are supported by experimental results and theoretical calculations. This work demonstrates the importance of aromaticity relay with the successive decrease of energy in reactions and will stimulate efforts in exploiting the vital role of aromaticity in synthetic chemistry.

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Fig. 1: Aromaticity relay strategy for ring contraction.
Fig. 2: Synthesis and characterization of precursor 1, [2 + 2] cycloaddition products 2a–2c and ring-contraction products 3a–3c.
Fig. 3: DFT calculations for mechanistic investigation.
Fig. 4: Control experiments and the isolation of key intermediates 4A.
Fig. 5: Aromaticity evaluation of model compounds 2a′, 4A′ and 3a′ by theoretical criteria.
Fig. 6: Chemical stability and optical properties.

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Data availability

All characterization data and experimental protocols are included in this Article and/or the Supplementary Information. Details of the synthesis and characterization of compounds S-1, S-2, L1, 2a–2c, 3a–3c, 4A, 5a, 5b and 6a can be found in the Supplementary Information. For general information, synthesis and characterization, see Supplementary Information, pages 2–13. For control experiments, see Supplementary Figs. 1–3. For crystallographic analysis, see Supplementary Figs. 4–10 and Supplementary Tables 1–10. For thermal stability tests, see Supplementary Table 11. For kinetic study, see Supplementary Fig. 11. For the mechanism for the formation of compound 1, see Supplementary Scheme 1. For computational methods, see Supplementary Figs. 12–23. For NMR spectra and ESI-MS spectra, see Supplementary Figs. 24–70. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under accession numbers 2103042 (2a), 2103166 (3a), 2103167 (3b), 2103168 (3c), 2103171 (4A), 2103169 (5b) and 2103170 (6a). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This work was supported by the Natural Science Foundation of China (numbers 22071206, 21931002 and 92156021), the Natural Science Foundation of Fujian Province of China (number 2020J01025), the Shenzhen Science and Technology Innovation Committee (number JCYJ20200109140812302) and the Guangdong Provincial Key Laboratory of Catalysis (number 2020B121201002).

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Author notes

  1. These authors contributed equally: K. Zhuo, Y. Liu.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Kaiyue Zhuo, Yanan Liu, Kaidong Ruan, Yu-Mei Lin & Haiping Xia

  2. Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, China

    Yuhui Hua & Haiping Xia

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  1. Kaiyue Zhuo
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Contributions

H.X. and Y.-M.L. conceived the project. K.Z. and Y.L. performed the experiments. K.Z., Y.L., H.X. and Y.-M.L. analysed and interpreted the experimental data. K.R. and Y.H. designed and performed the theoretical calculations. K.Z., Y.L. and Y.-M.L. prepared the manuscript. Y.L. and K.Z. prepared the Supplementary Information. All the authors discussed the results and contributed to the preparation of the final manuscript.

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Correspondence to Yu-Mei Lin or Haiping Xia.

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The authors declare no competing interests.

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Nature Synthesis thanks Daniel Mindiola and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–70, Tables 1–11, Scheme 1, Computational Methods, Discussion.

Supplementary Data 1

Crystallographic data for compound 2a; CCDC 2103042.

Supplementary Data 2

Crystallographic data for compound 3a; CCDC 2103166.

Supplementary Data 3

Crystallographic data for compound 3b; CCDC 2103167.

Supplementary Data 4

Crystallographic data for compound 3c; CCDC 2103168.

Supplementary Data 5

Crystallographic data for compound 4A; CCDC 2103171.

Supplementary Data 6

Crystallographic data for compound 5b; CCDC 2103169.

Supplementary Data 7

Crystallographic data for compound 6a; CCDC 2103170.

Supplementary Data 8

Cartesian coordinate-optimized structures for calculations.

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Zhuo, K., Liu, Y., Ruan, K. et al. Ring contraction of metallacyclobutadiene to metallacyclopropene driven by π- and σ-aromaticity relay. Nat. Synth 2, 67–75 (2023). https://doi.org/10.1038/s44160-022-00194-2

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