Scientists of the Zelinsky Institute published a review on radical reactions of the functionalization of heterocycles with heteroatom-centered radicals

In the last decade, free radicals have found a wide application in the functionalization of unsaturated compounds such as alkenes, alkynes, and arenes by free radical addition to multiple C=C bonds. In these processes, the intermolecular attack of free radicals on aromatic substrates is a fundamental problem due to the relatively high resistance of the aromatic p-system to addition reactions compared to C=C bonds in alkenes. Free radical functionalization of heterocycles is of particular interest due to the diversity of their structures and chemical properties, as well as their importance for medicinal chemistry, agrochemistry, and materials science.

Scientists from the Laboratory for the Study of Homolytic Reactions of the ZIOC published a review summarizing the results of modern studies on the addition of heteroatom-centered radicals to heterocyclic systems. The review considers the problems and prospects of the addition of O-, N-, S-/Se-, and P-radicals with an emphasis on consideration of the mechanisms of the discussed reactions and modern methods of electrochemistry and photoredox catalysis for the generation of free radicals.

Source:

Alexander S. Budnikov, Igor B. Krylov, Olga M. Mulina, Dmitry A. Lapshin, Alexander O. Terent’ev CH-Functionalization of Heterocycles with the Formation of C-O, C-N, C-S/Se, and C-P Bonds by Intermolecular Addition of Heteroatom-Centered Radicals // Adv. Synth. Catal., 2023, accepted manuscript. DOI: 10.1002/adsc.202300144.