Radical Hydrogen Atom Transfer Reactions to Unactivated p-Systems

Abstract

We demonstrate water activation by a photocatalytic phosphine-mediated radical process, generating a _PR3-H2Oradical cation intermediate, where both hydrogen atoms are used in the following chemical transformation through sequential cleavage of the O-H bonds.¹ We will show how phosphoranyl radicals can be turned into super electron donors.² Moreover, P-radical cations can also be used for activation of ^nitroarenes3 and it will be discussed that nitroarenes are radical oxygenation reagents for Fe-catalyzed alkene hydrations.^{4 Further} , a new radical amidation reagent is introduced and applications for the hydroamidation of complex alkenes will be demonstrated.⁵ Finally, Fe-catalyzed hydrohalogenations of alkenes are discussed.⁶

References

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[2] M.-A. Wiethoff, L. Lezius, A. Studer, Angew. Chem. Int. Ed.2025, 62, e202501757.

[3] J. Zhang, C. Mück-Lichtenfeld, M. A. Wiethoff, A. Studer, Angew. Chem. Int. Ed. 2024, 62, e202416726.

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[5] M. Huang, C. G. Daniliuc, A. Studer, Nat. Synth. 2025, 9, in press (DOI: 10.1038/s44160-025-00792-w).

[6] J. Elfert, N. L. Frye, I. Rempel, C. G. Daniliuc, A. Studer, Nat. Commun. 2024, 15, 7230.