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The design of PINO-like hydrogen-atom-transfer catalysts

Nature Reviews Chemistry volume 7, pages 653–666 (2023)Cite this article

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Abstract

Phthalimide-N-oxyl (PINO) is a valuable hydrogen-atom-transfer (HAT) catalyst for selective C–H functionalization. To advance and optimize PINO-catalysed HAT reactions, researchers have been focused on modifying the phthalimide core structure. Despite much effort and some notable advances, the modifications to date have centred on optimization of a single parameter of the catalyst, such as reactivity, solubility or stability. Unfortunately, the optimization with respect to one parameter is often associated with a worsening of the others. The derivation of a single catalyst structure with optimal performance across multiple parameters has therefore remained elusive. Here we present an analysis of the structure–activity relationships of PINO and its derivatives as HAT catalysts, which we hope will stimulate further development of PINO-catalysed HAT reactions and, ultimately, lead to much improved catalysts for real-world applications.

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Fig. 1: Three strategies of PINO generation from oxidation of NHPI.
Fig. 2: Thermodynamic aspects (BDE analysis) of PINO-type HAT mediators.
Fig. 3: Design of a more reactive PINO-type catalyst through EWG polarization effect.
Fig. 4: Efforts towards developing regio- or enantioselective PINO species.
Fig. 5: Development of more lipophilic PINO catalysts.
Fig. 6: Development of more stable PINO-type species.
Fig. 7: The base effect on PINO-catalysed benzylic alcohol oxidation and revised mechanism of its decomposition.
Fig. 8: Key considerations for optimization of PINO-catalysed oxidations.

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Acknowledgements

C.R.J.S. and S.M. acknowledge the financial support from the National Science Foundation (CBET-2033714), and the University of Michigan. D.A.P. acknowledges the financial support from the Natural Sciences and Engineering Research Council of Canada (RGPIN-2022-05058). C.Y. acknowledges a Rackham pre-doctoral fellowship from the University of Michigan.

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  1. Willard Henry Dow Laboratory, Department of Chemistry, University of Michigan, Ann Arbor, MI, USA

    Cheng Yang, Sahil Arora, Stephen Maldonado & Corey R. J. Stephenson

  2. Program in Applied Physics, University of Michigan, Ann Arbor, MI, USA

    Stephen Maldonado

  3. Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario, Canada

    Derek A. Pratt

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C.Y., S.M., D.A.P. and C.R.J.S. contemplated the topic and structure of the Review. C.Y. conducted the literature research. All authors contributed to the discussion of the content and wrote or edited the manuscript.

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Yang, C., Arora, S., Maldonado, S. et al. The design of PINO-like hydrogen-atom-transfer catalysts. Nat Rev Chem 7, 653–666 (2023). https://doi.org/10.1038/s41570-023-00511-z

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