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Metallaphotoredox catalysis for sp3 C–H functionalizations through single-electron transfer

Nature Catalysis volume 7, pages 963–976 (2024)Cite this article

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Abstract

Metallaphotoredox catalysis merging photocatalysis and transition metal catalysis is now the most efficient platform for sp3 C–H functionalizations due to its very efficient activation and transformation capability. In such a process, photocatalysis is usually in charge of C–H bond activation to generate an sp3-hybridized carbon-centred radical, whereas transition metal catalysis is in charge of the subsequent transformation of this radical. Here we review advances in sp3 C–H functionalizations under matallaphotoredox catalysis via photocatalytic single-electron transfer mechanisms as opposed to hydrogen atom transfer processes. The delineation of these advancements is initially organized according to distinct sp3 C–H bonds and subsequently categorized by various transition metal catalytic systems. We encompass a thorough exploration of diverse metallaphotoredox catalysis strategies, along with their synthetic applications and mechanisms. Similarities and differences between these strategies are described to inspire new reaction designs, thus promoting further development of this field.

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Fig. 1: Excitation of a photocatalyst and its participation in metallaphotoredox catalysis.
Fig. 2: α-sp3 C–H activation of amines.
Fig. 3: α-functionalizations of anilines.
Fig. 4: α-functionalizations of amines.
Fig. 5: α-functionalizations of amines.
Fig. 6: α-functionalizations of anilines.
Fig. 7: Functionalizations of allylic C–H.
Fig. 8: Functionalizations of benzylic C–H.

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Acknowledgements

J.Z. thanks the Jining Medical University High-Level Research Foundation for financial support (600497001 and 600497002). M.R. thanks the Office of Sponsored Research at King Abdullah University of Science and Technology in Saudi Arabia for financial support (URF/1/4405).

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  1. Department of Chemistry, School of Pharmacy, Jining Medical University, Rizhao, China

    Jingchang Zhang

  2. KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Magnus Rueping

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  1. Jingchang Zhang
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  2. Magnus Rueping
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Correspondence to Jingchang Zhang or Magnus Rueping.

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Zhang, J., Rueping, M. Metallaphotoredox catalysis for sp3 C–H functionalizations through single-electron transfer. Nat Catal 7, 963–976 (2024). https://doi.org/10.1038/s41929-024-01215-3

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