Photoredox catalysis has recently emerged as a powerful synthetic platform for accessing complex chemical structures through non-traditional bond disconnection strategies that proceed through free-radical intermediates. Such synthetic strategies have been used for a range of organic transformations; however, in carbohydrate chemistry they have primarily been applied to the generation of oxocarbenium ion intermediates in the ubiquitous glycosylation reaction. In this Review, we present more intricate light-induced synthetic strategies to modify native carbohydrates through homolytic C–H and C–C bond cleavage. These strategies allow access to glycans and glycoconjugates with profoundly altered carbohydrate skeletons, which are challenging to obtain through conventional synthetic means. Carbohydrate derivatives with such structural motifs represent a broad class of natural products integral to numerous biochemical processes and can be found in active pharmaceutical substances. Here we present progress made in C–H and C–C bond activation of carbohydrates through photoredox catalysis, focusing on the operational mechanisms and the scope of the described methodologies.
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Financial support from FORMAS (grant no. 2019-01269), the Swedish Research Council (grant no. 2020-04764), the Olle Engkvist Foundation, the Wenner-Gren Foundations, the Magnus Bergvall Foundation and the KTH Royal Institute of Technology to M.D.K. is gratefully acknowledged. Financial support to E.V.S. from the Russian Science Foundation (project no. 21-73-10211) is gratefully acknowledged.
The authors declare no competing interests.
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Shatskiy, A., Stepanova, E.V. & Kärkäs, M.D. Exploiting photoredox catalysis for carbohydrate modification through C–H and C–C bond activation. Nat Rev Chem 6, 782–805 (2022). https://doi.org/10.1038/s41570-022-00422-5