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Modular bismacycles for the selective C–H arylation of phenols and naphthols

Nature Chemistry volume 12, pages 260–269 (2020)Cite this article

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Abstract

Given the important role played by 2-hydroxybiaryls in organic, medicinal and materials chemistry, concise methods for the synthesis of this common motif are extremely valuable. In seeking to extend the lexicon of synthetic chemists in this regard, we have developed an expedient and general strategy for the ortho-arylation of phenols and naphthols using readily available boronic acids. Our methodology relies on in situ generation of a uniquely reactive Bi(v) arylating agent from a bench-stable Bi(iii) precursor via telescoped B–to–Bi transmetallation and oxidation. By exploiting reactivity that is orthogonal to conventional metal-catalysed manifolds, diverse aryl and heteroaryl partners can be rapidly coupled to phenols and naphthols under mild conditions. Following arylation, high-yielding recovery of the Bi(iii) precursor allows for its efficient re-use in subsequent reactions. Mechanistic interrogation of each key step of the methodology informs its practical application and provides fundamental insight into the underexploited reactivity of organobismuth compounds.

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Fig. 1: Occurrence and Bi(v)-mediated synthesis of 2-hydroxybiaryls.
Fig. 2: Synthesis of a universal bismacycle(iii) precursor.
Fig. 3: One-pot, Bi(v)-mediated arylation of phenols and naphthols.
Fig. 4: Bi(v)-mediated arylation enables concise synthesis and diversification of biologically active compounds without substrate prefunctionalization.
Fig. 5: Preliminary mechanistic investigations.

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Data availability

Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers 1904059 (1-OTs), 1904060 (2a), 1904061 (2b), 1904062 (2c), 1904063 (2e), 1904064 (2g), 1904065 (2h), 1904066 (2i), 1904069 (2j), 1904067 (2k), 1904068 (2m), 1904070 (2u), 1904071 (2v), 1904072 (9) and 1904073 (50). Copies of the data can be obtained free of charge at www.ccdc.cam.ac.uk/data_request/cif. The authors declare that all other data supporting the findings of this study are available within the paper and its Supplementary information.

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Acknowledgements

This work was supported by The University of Nottingham.

Author information

Authors and Affiliations

  1. GSK Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, Nottingham, UK

    Mark Jurrat, Lorenzo Maggi & Liam T. Ball

  2. School of Chemistry, University of Nottingham, University Park, Nottingham, UK

    Mark Jurrat, Lorenzo Maggi, William Lewis & Liam T. Ball

  3. School of Chemistry, The University of Sydney, Sydney, Australia

    William Lewis

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Contributions

M.J. and L.T.B. conceived this work. M.J. and L.M. performed the experiments and analysed the data. W.L. acquired and solved X-ray diffraction data. L.T.B. wrote the manuscript with input from M.J. and L.M.

Corresponding author

Correspondence to Liam T. Ball.

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Competing interests

Bismacycle 1-OTs has been made commercially available via Key Organics. The sales revenue that is returned to the University of Nottingham covers the costs of commercialization; the authors do not receive profit from any of the sales that are made.

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Supplementary information

Supplementary information

Synthetic procedures, characterization data, crystallographic data tables and NMR spectra.

Crystallographic data

Crystallographic data for compound 1-OTs. CCDC reference 1904059.

Crystallographic data

Crystallographic data for compound 2a. CCDC reference 1904060.

Crystallographic data

Crystallographic data for compound 2b. CCDC reference 1904061.

Crystallographic data

Crystallographic data for compound 2c. CCDC reference 1904062.

Crystallographic data

Crystallographic data for compound 2e. CCDC reference 1904063.

Crystallographic data

Crystallographic data for compound 2g. CCDC reference 1904064.

Crystallographic data

Crystallographic data for compound 2h. CCDC reference 1904065.

Crystallographic data

Crystallographic data for compound 2i. CCDC reference 1904066.

Crystallographic data

Crystallographic data for compound 2j. CCDC reference 1904069.

Crystallographic data

Crystallographic data for compound 2k. CCDC reference 1904067.

Crystallographic data

Crystallographic data for compound 2m. CCDC reference 1904068.

Crystallographic data

Crystallographic data for compound 2u. CCDC reference 1904070.

Crystallographic data

Crystallographic data for compound 2v. CCDC reference 1904071.

Crystallographic data

Crystallographic data for compound 9. CCDC reference 1904072.

Crystallographic data

Crystallographic data for compound 50. CCDC reference 1904073.

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Jurrat, M., Maggi, L., Lewis, W. et al. Modular bismacycles for the selective C–H arylation of phenols and naphthols. Nat. Chem. 12, 260–269 (2020). https://doi.org/10.1038/s41557-020-0425-4

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