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ORGANOBISMUTH CHEMISTRY

Heavy metal orchestration

Nature Chemistry volume 12, pages 223–224 (2020)Cite this article

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Many current methods to prepare 2-hydroxybiaryls require the prefunctionalization of phenol groups or show limited substrate scope. Now, use of a pentavalent sulfone-bridged bismacycle, formed in situ by telescoped boron-to-bismuth transmetallation and oxidation, allows the direct and regioselective ortho-arylation of unprotected phenols.

Bismuth, the 83rd element of the periodic table and last naturally occurring member of the pnictogen family, is a non-toxic and non-radioactive heavy metal. Organobismuth compounds have long been known to be a versatile class of organometallic species9,10. In 1980, Barton and Motherwell reported that pentavalent arylbismuth(v) reagents can be used for the arylation of phenols — but the extent to which the reaction occurs at the Cortho site, versus the O atom of the hydroxyl group, is highly dependent on the nature of the organobismuth species and the reaction conditions11. In addition, this method requires the cumbersome isolation of pentavalent bismuth(v) species or the presence of a strong base. In contrast, the present study by Ball and co-workers8 reports a one-pot telescoped boron-to-bismuth transmetallation and oxidation sequence, forming a bismacycle species (A) that efficiently carries out the regioselective ortho-arylation of unprotected phenols 1 (Fig. 1b). This protocol does not require the installation of a directing group or a transition metal catalyst, operates under air in non-anhydrous conditions and completely prevents the formation of O-arylated products.

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Fig. 1: Development of a general method for the direct and regioselective ortho-arylation of unprotected phenols via a telescoped one-pot boron-to-bismuth transmetallation and oxidation sequence.

References

  1. Cramer, J., Sager, C. P. & Ernst, B. J. Med. Chem. 62, 8915–8930 (2019).

    Article  CAS  Google Scholar 

  2. Roughley, S. D. & Jordan, A. M. J. Med. Chem. 54, 3451–3479 (2011).

    Article  CAS  Google Scholar 

  3. McGrath, N. A., Brichacek, M. & Njardarson, J. T. J. Chem. Educ. 87, 1348–1349 (2010).

    Article  CAS  Google Scholar 

  4. Brown, D. G. & Boström, J. J. Med. Chem. 59, 4443–4458 (2016).

    Article  CAS  Google Scholar 

  5. Quideau, S., Deffieux, D., Douat-Casassus, C. & Pouységu, L. Angew. Chem. Int. Ed. 50, 586–621 (2011).

    Article  CAS  Google Scholar 

  6. Hassan, J., Sévignon, M., Gozzi, C., Schulz, E. & Lemaire, M. Chem. Rev. 102, 1359–1469 (2002).

    Article  CAS  Google Scholar 

  7. Huang, Z. & Lumb, J.-P. ACS Catal. 9, 521–555 (2019).

    Article  CAS  Google Scholar 

  8. Jurrat, M., Maggi, L., Lewis, W. & Ball, L. T. Nat. Chem. https://doi.org/10.1038/s41557-020-0425-4 (2020).

  9. Gagnon, A., Dansereau, J. & Le Roch, A. Synthesis 49, 1707–1745 (2017).

    Article  CAS  Google Scholar 

  10. Gagnon, A., Benoit, E. & Le Roch, A. in Science of Synthesis Knowledge Updates Vol. 4, 1–111 (Thieme, 2018).

  11. Barton, D. H. R., Lester, D. J., Motherwell, W. B. & Barros Papoula, M. T. J. Chem. Soc. Chem. Commun. 246–247 (1980).

  12. Suzuki, H., Murafuji, T. & Azuma, N. J. Chem. Soc. Perkin Trans. I 1593–1600 (1992).

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  1. Département de Chimie, Université du Québec à Montréal, Montréal, Québec, Canada

    Adrien Le Roch & Alexandre Gagnon

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  1. Adrien Le Roch
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Correspondence to Alexandre Gagnon.

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Le Roch, A., Gagnon, A. Heavy metal orchestration. Nat. Chem. 12, 223–224 (2020). https://doi.org/10.1038/s41557-020-0434-3

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