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Photoredox‐Catalyzed Hydroalkylation of C(sp 3 )–H Acids
Author(s) -
Morris Avery O.,
O'Brien Tegan E.,
Barriault Louis
Publication year - 2025
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202501148
Abstract We present a detailed study on a photoredox catalysis platform that directly engages 1,3‐dicarbonyl C(sp 3 )–H acids toward radical reactions. This platform enables redox‐neutral hydroalkylation and cross‐coupling, as well as oxidative transformations that demonstrably improve on the prior state of the art. Herein, we present interrogations of the underlying catalytic cycle and mechanism for this platform through kinetic, thermodynamic, and computational studies. The present investigations also demonstrate the key role of lithium trifluoroacetate under complementary Ce‐containing and Ce‐free photoredox conditions to enable ligand‐to‐metal charge transfer (LMCT) or multi‐site proton‐coupled electron transfer (MS‐PCET) activations, respectively.