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  • Review Article
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Radical cascade reactions triggered by single electron transfer

Nature Reviews Chemistry volume 1, Article number: 0077 (2017) Cite this article

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Abstract

The rapid generation of molecular complexity from simple starting materials is of paramount importance in synthetic chemistry. The unique combination of high reactivity and high selectivity often associated with open-shell intermediates makes radical chemistry ideal for cascade reactions, in which simple substrates undergo a series of processes involving bond formation (and bond cleavage) to give complex, high-value products. Crucially, radical cascade reactions can greatly diminish the time, cost and amount of waste associated with complex target synthesis. Recent exciting advances in the field of radical chemistry initiated by single electron transfer (SET) have led to a considerable upward shift in our ability to design powerful new cascade reactions. This Review highlights recent advances in the development of radical cascades, triggered by SET processes, that deliver molecular constructs of importance in medicine and biology.

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Figure 1: Introduction to SET radical cascades.
Figure 2: Oxidative SET radical cascades mediated by manganese(III).
Figure 3: Oxidative SET radical cascades mediated by silver, iron and electrochemistry.
Figure 4: Reductive SET radical cascades mediated by samarium(II).
Figure 5: Reductive SET radical cascades mediated by titanium and copper.
Figure 6: Oxidative SET radical cascades mediated by photoredox catalysis.
Figure 7: Reductive radical cascades mediated by photoredox catalysis.

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Acknowledgements

The authors thank the Engineering and Physical Sciences Research Council (EPSRC; studentship to M.P. and an Established Career Fellowship to D.J.P. (Grant No. EP/M005062/1) and the University of Manchester (President's Scholarship to H.H.).

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  1. School of Chemistry, Oxford Road, University of Manchester, Manchester, M13 9PL, UK

    Mateusz P. Plesniak, Huan-Ming Huang & David J. Procter

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  1. Mateusz P. Plesniak
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M.P. and H.H. researched data for the Review. All authors contributed to the discussion, writing and editing of the Review.

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Correspondence to David J. Procter.

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Glossary

Single electron transfer

(SET). Step in a chemical reaction characterized by donation or removal of an electron.

Captodative stabilization

Increased stability of a carbon-centred radical resulting from the combined effect of electron-withdrawing and electron-donating groups attached to the radical centre.

Proton-coupled electron transfer

(PCET). Class of chemical reactions that involves the transfer of an electron and proton in a concerted elementary step.

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Plesniak, M., Huang, HM. & Procter, D. Radical cascade reactions triggered by single electron transfer. Nat Rev Chem 1, 0077 (2017). https://doi.org/10.1038/s41570-017-0077

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