The generation of carbon radicals by halogen-atom and group transfer chemistry is one the most applied methods in synthetic radical chemistry.¹ The broad availability of organic halides as well as alcohol/thiol derivatives provides a large pool of commercial materials for divergent functionalizations.

 

These reactions have been generally approached using radicals able to form strong bonds with halogen/O/S atoms and of nucleophilic character to stabilize the transition state by charge-transfer.² Tin and silicon species are the most used and versatile reagents to achieve this, despite their cost and toxicity profile.^1,3 

 

In this presentation, I will discuss some recent work from my group aimed at developing a novel approach for carbon radical generation using H-atoms (H•) as the abstracting species. This H-atom transfer reactivity profiles differs from normal HAT reactions in the way that the H-atom is not abstracted but is the key abstracting species in the process.⁴

[1] (a) Crespi, S.; Fagnoni, M. Chem. Rev. 2020, 120, 9790. (b) Denes, F.; Schiesser, C. H.; Renaud, P. Chem. Soc. Rev. 2013, 42, 7900.
[2] Constantin, T; Julia, F.; Leonori, D. Chem. Rev. 2022, 122, 2292.
[3] Baguley, P. A.; Walton, J. C. Angew. Chem. Int. Ed. 1998, 37, 3082.
[4] unpublished results.