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Light-induced transition-metal-catalysed hydrogen atom transfer in organic transformations

Abstract

Selective conversion of C–H bonds into high-value functional groups is a highly desirable process. Hydrogen atom transfer (HAT) is a powerful approach towards this goal by offering straightforward access to open-shell radical intermediates directly from R–H bonds. Recently, a subclass of photocatalysis referred to as visible-light-induced transition metal (TM) catalysis has emerged as a distinctive synthetic tool. This enables TMs to serve a dual role: capturing light energy and driving catalytic transformations. This dual functionality has been increasingly utilized to execute HAT without requiring an external photosensitizer. Although cooperative photocatalysis involving photoredox and TM catalysis contributed to early developments in this area, visible-light-induced TM catalysis offers direct and versatile approaches to C–H functionalization. In the past few years, this methodology has been extensively used to execute HAT. Here we describe the early development and recent advances of photoexcited-transition-metal-catalysed HAT processes.

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Fig. 1: Thermodynamic and kinetic driving factors for HAT, and modes of HAT in TM catalysis.
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Fig. 2: Palladium catalysis via tethered strategies.
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Fig. 3: Palladium catalysis via non-tethered strategies.
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Fig. 4: Copper catalysis via tethered strategies.
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Fig. 5: Copper catalysis via non-tethered strategies.
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Fig. 6: Cerium catalysis.
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Fig. 7: Iron catalysis.
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Fig. 8: Ru, Co and Cr catalysis.
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Acknowledgements

V.G., K.M. and A.B.D. are grateful to the National Institutes of Health (R35GM156632) and The Welch Foundation (AT-0041) for financial support. H.N. and R.H. are grateful to the Higher Education and Science Committee (grant 22RL-017).

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V.G. provided key discussions and ideas and reviewed the text. K.M., A.B.D., H.N. and R.H. collected literature reports and wrote the text.

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Correspondence to Vladimir Gevorgyan.

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Mukherjee, K., Ben David, A., Nikoghosyan, H. et al. Light-induced transition-metal-catalysed hydrogen atom transfer in organic transformations. Nat Catal 8, 1146–1158 (2025). https://doi.org/10.1038/s41929-025-01431-5

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