Browsing by Subject "Synthetic methodology"

Now showing 1 - 3 of 3
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    Dual-role iron species in photoelectrocatalytic radical trifluoromethylation with trifluoroacetates
    (Springer Nature, 2026-02-20) Juliá Hernández, Francisco; Fernández-García, Sara; Cuadros, Sara; Bosque, Irene; González-Gómez, José C.; Química Inorgánica; Facultad de Química
    Trifluoromethylation remains a fundamental transformation in drug discovery, underpinning many top-selling pharmaceuticals. Emerging developments in iron ligand-to-metal charge transfer (LMCT) catalysis have redefined fluoroalkylation chemistry by unlocking the repurposing of readily available trifluoroacetates as radical trifluoromethyl sources. Recent (hetero)arene trifluoromethylation methods generally require stoichiometric inorganic oxidants to turnover photoactive iron catalysts, thereby limiting their broader applicability. Herein, we present an integrated photoelectrocatalytic strategy employing in situ-generated multifunctional iron species to achieve C(sp²)–H trifluoromethylation without stoichiometric oxidants and generating only traceless byproducts. Mechanistic studies identify catalytically active iron species exhibiting a dual synergistic function: promoting the photodecarboxylation of trifluoroacetates and mediating catalytic redox turnover. This protocol offers mild, tunable, and scalable conditions powered by visible light and electric current. It features a broad substrate scope, enabling the functionalization of diverse (hetero)cyclic scaffolds, including challenging electron-rich and easily oxidizable substrates, thus demonstrating its potential for sustainable late-stage modification in pharmaceutical synthesis.
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    Fe-LMCT photodecarboxylation for (hetero)arene chloro- and bromodifluoromethylation: rapid access to aromatic acyl fluorides
    (American Chemical Society, 2026-04-20) Juliá Hernández, Francisco; Fernández-García, Sara; Visiedo-Jiménez, Paula; Química Inorgánica; Facultad de Química
    Chloro- and bromodifluoromethyl groups (CF2X) offer complementary properties to other fluorinated substituents in modulating biological functionality and provide versatile synthetic handles for postfunctionalization. However, their widespread use remains limited by the scarcity of practical halodifluoromethylating reagents. Here, we report a photoinduced Fe-catalyzed strategy that repurposes readily available chloro- and bromodifluoroacetates as traceless radical precursors for (hetero)arene C–H halodifluoroalkylations. The resulting products exhibit broad synthetic versatility, enabling streamlined one-pot access to valuable acyl fluoride synthons.
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    Photocatalytic pathways for hydrochlorination
    (Nature Research, 2025-01-02) Juliá Hernández, Francisco; Química Inorgánica; Facultades de la UMU::Facultad de Química
    Iron photocatalysis, in conjunction with a cooperative radical mechanism, enables the anti-Markovnikov hydrochlorination of unsaturated feedstocks, using light as an energy source.