Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Photochemistry

Radical arenes

Nature Chemistry volume 15, pages 3–4 (2023)Cite this article

Subjects

Radical-mediated functionalization streamlines access to complex synthetic targets. Now, a sulfonium-based donor–acceptor pair enables photoinduced charge-transfer interactions to access electronically diverse aryl radicals. Reaction with enol ethers or isocyanide provides a metal-free method for arene functionalization.

This elegantly simple design is akin to nature’s alkylating agent, S-adenosyl methionine, in that it employs cationic arylsulfonium salts and harnesses subsequent radical intermediates as key design elements for enabling broadly useful reactivity. Conversely, in this approach arylsulfonium salts are readily accessed by Pummerer-inspired C–H functionalization of arenes — with high para-selectivity due to selective rearomatization of a charged intermediate7. These salts have previously been studied as electrophilic partners in Pd-catalysed cross-coupling8. However, a key insight made by Procter and co-workers is that these arylsulfonium salts could also serve as excellent acceptors within EDA complexes. This aryl radical strategy complements SN2-based methods that enable access to alkyl radicals by EDA reactivity9.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Site-selective arene C–H cyanation and alkylation mediated by radicals.

References

  1. Blakemore, D. C. et al. Nat. Chem. 10, 383–394 (2018).

    Article  CAS  Google Scholar 

  2. Wencel-Delord, J. & Glorius, F. Nat. Chem. 5, 369–375 (2013).

    Article  CAS  Google Scholar 

  3. Campeau, L. C. & Hazari, N. Organometallics 38, 3–35 (2019).

    Article  CAS  Google Scholar 

  4. Calloway, N. O. Chem. Rev. 17, 327–392 (1935).

    Article  CAS  Google Scholar 

  5. Hartwig, J. F. J. Am. Chem. Soc. 138, 2–24 (2016).

    Article  CAS  Google Scholar 

  6. Dewanji, A. et al. Nat. Chem. https://doi.org/10.1038/s41557-022-01092-y (2022).

  7. Juliá, F. et al. J. Am. Chem. Soc. 143, 16041–16054 (2021).

    Article  Google Scholar 

  8. Berger, F. et al. Nature 567, 223–228 (2019).

    Article  CAS  Google Scholar 

  9. Crisenza, E. M. G., Mazzarella, D. & Melchiorre, P. J. Am. Chem. Soc. 142, 5461–5476 (2020).

    Article  CAS  Google Scholar 

  10. Aukland, M. H., Šiaučiulis, M., West, A., Perry, G. J. P. & Procter, D. J. Nat. Catal. 3, 163–169 (2020).

    Article  CAS  Google Scholar 

  11. Culkin, D. A. & Hartwig, J. F. Acc. Chem. Res. 36, 234–245 (2003).

    Article  CAS  Google Scholar 

  12. Zhao, D., Xu, P. & Ritter, T. Chem. 5, 97–107 (2019).

    Article  CAS  Google Scholar 

Download references

Author information

Author notes

  1. Twitter: @nagiblab

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA

    Taylor N. Bednar & David A. Nagib

Authors
  1. Taylor N. Bednar
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. David A. Nagib
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to David A. Nagib.

Ethics declarations

Competing interests

The authors declare no competing interests.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Bednar, T.N., Nagib, D.A. Radical arenes. Nat. Chem. 15, 3–4 (2023). https://doi.org/10.1038/s41557-022-01109-6

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41557-022-01109-6

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing